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Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis
Optik - International Journal for Light and Electron Optics 185 (2019) 191–198
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Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis
T
Guannan Qua,c, Minsi Xina, Qiang Jiaa, Pengcheng Caia, Guangyong Jinb, Yunquan Zhoua, Chunyu Liua, Yong Tana, Ye Zhanga, Zhihai Yaoa, Aoran Fenga, ⁎ Hongxing Caia,c, a
School of Science, Changchun University of Science and Technology, Changchun, 130022, China Jilin Key Laboratory of Solid-State Laser Technology and Application, Changchun University of Science and Technology, Changchun, 130022, China c Key laboratory of Jilin Province for Spectral Detection Science and Technology, Changchun University of Science and Technology, Changchun, 130022, China b
A R T IC LE I N F O
ABS TRA CT
Keywords: All-trans-β-carotene Density functional theory Phase transition Raman scattering cross section
Raman and absorption features all-trans-β-carotene (β-Car) liquefied in dimethyl sulfoxide (DMSO) of 10−6 concentration at temperature range from 333K to 263K are recorded. The usage of density functional theory (DFT) calculations could meticulously anticipate the molecular vibration mechanism. The calculation of CC bond length alternation (BLA) and graphic illustration of the highest occupied molecular orbital (HOMO) of β-Car can help decipher the vibration mechanism during phase transition. The Raman scattering cross section (RSCS) of the CC single and double bonds roughly increases when temperature decreases during pure liquid- solid phase condition due to extended effective conjugation length (ECL). The RSCS sharply drops during the phase transition because the β rings are very likely rotated from 0° to 90°. Electronic transition energy (0-0) of absorption spectra declining lead to the amplified resonance effect. This research is counted upon to be valuable by using DFT calculations to investigate the influence of phase transition on resonance Raman character of β-Car.
1. Introduction Carotenoids are treated as organic biomolecules which act a pivotal part in biology photosynthesis [1]. Their singlet and triplet type energy transfer manner plays a vital role in light reaction, exposure and harvesting [1,2]. β-Car is a conjugated molecule built from 11 alternative single and double bond units. Its π electron delocalization is protracted into the β rings which is located at the end of the chain and is always regarded as a referential model in biophysics and biochemistry filed. Carotenoids could carry out structural counterpoise in light-harvesting due to the assembly of pigment-protein complexes [3]. Their linear conjugated polyene structure makes it possible to accomplish the energy transfer in singlet and excited states [2,4,5]. Comprehensive researches showed crux in surmising the entire electronic structure of β-car [6]. Copious representations of resonance Raman and absorption spectra of β-Car have already been developed [1,7]. The optical features of carotenoids could be powerfully affected by ECL [7]. Resonance Raman spectra provide the support on better apprehending the relationship between the structure and the electronic states of the polyene in photosynthetic process [8]. Natural bond orbital (NBO) theory could be applied to supervise the evolvement of electron delocalization. The comparably feeble orbital ⁎
Corresponding author at: School of Science, Changchun University of Science and Technology, Changchun, 130022, China. E-mail address: [email protected] (H. Cai).
https://doi.org/10.1016/j.ijleo.2019.03.109 Received 2 February 2019; Accepted 19 March 2019 0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
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interactions led to the reduction of conjugation efficacy for the polyeneynes [9,10]. Conformational fluctuations of β-Car induced by solvent effect can largely sway the bandwidth properties [11]. Some investigations on carotenoid optical response influenced by external field have already been implemented. Raman and absorption properties of polyenes changed a lot with different pressure and solvent effects [12,13]. Moreover, the multitudinous temperature dependent Raman and absorption profiles of β-Car reveal the important phenomenon [14–16]. However, the analysis is mostly fixated on the frequency alteration in various situation but pay less attention to Raman intensity. In addition, Raman intensity properties of β-Car on the condition of phase transition induced by temperature is still limited. Some Raman explorations on β-Car manifest that the electron-phonon coupling combined with coherent weakly damped electron lattice vibrations had large efforts to Raman intensity [17,18]. Parameter variations caused by the environment induce Raman intensity changed during phase transition are still largely unknown. To further dig out the micro-phenomenon, quantum chemistry calculations are utilized to further interpret these observations. In our research, the absorption and Raman properties of β-Car molecule in DMSO at temperature range from 333 K to 263 K have been scrutinized. The intensity of Raman spectra and electronic energy of absorption gives information that the effective conjugation length and π electron delocalization will straightforwardly influence the vibration character. DFT calculations, using the B3LYP functional and theoretical investigation helps analyze the molecular structure. CC bond at each end of the chain could be easily revolved during intricate environment. This work provides an idea for modulating temperature to change Raman intensity of carotenoid. It can also provide favorable information on molecular structure during phase transition through theoretical calculation. 2. Materials and methods 2.1. All-trans-β-carotene preperation β-Car (purity is ≥97.0%, C40H56) tested in this research was got from Sigma-Aldrich (St. Louis, MO). It should be stored at negative 20 ° in the lightless room and with no further purification. 2.2. Solvents preperation The β-Car was dissolved in DMSO (C2H6SO AR, 99.8%) and benzene (C6H6 anhydrous, analytical grade 99.5%) at a concentration of 2.1 × 10−6 M. The experiment should be carried out at once to prevent the solution further degradation. The 992 cm-1 line of benzene at a concentration of ˜10−7M was used as internal standard. 2.3. Raman and absorption spectroscopy The absorption spectra were explored using Agilent Technologies UV–vis-NIR Spectrophotometer (Cary-5000). The solution was injected in an enclosed quartz cuvette with 1 cm × 1 cm square. Raman spectra were acquired by a three-stage monochromator (Trivista 555 CRS, USA). A 5 mW Ar + laser with 532 nm wavelength was supplied the excitations and recorded in a nitrogen-flow cryostat. A back-illuminated CCD detector(Princeton Instruments Pylon 400)with 90° signal acquiring was installed with the whole equipment. The sample status was monitored through a 20 times objective lens with 0.12 numerical aperture. The scanning speed for absorption and Raman spectra are 1 nm step and 10cm−1/min, respectively. All the experiments were conducted in a dark room. 2.4. Computational approach The calculations of structure and vibrational spectroscopic characteristics were performed for β-car using the DFT approaches executed in the Gaussian09 series of programs [19]. The usage of B3LYP density functional combine with 6–31 G and 6–311 G (d,p) basis sets had a great contribution in this study. 3. Experiment results and discussion 3.1. DFT calculation about the β-Car structure The schematic and optimized geometry of the β-Car molecule obtained through B3LYP/6–311 G basis set is illustrated in Fig.1a and Fig.1b. The numbered carbon atoms are marked along the chain. The pattern of the chain is consist of 11 alternated single and double CC bonds with two β rings. The optimized lengths of CC bonds using B3LYP/6–31 G and 6–311 G (d,p) basis sets listed in Table1 represent well matching value. The deviation of length between single and double bond which is named as BLA optimized by B3LYP/6–311 G basis set show apparent rise at the tail of the chain, while it displays an decreasing trend in the center part (Fig.2). The larger BLA at end of the chain indicates that the bonds of incidental part of polyene chain is more unpredictable than the bonds at the center. To further dig out the optimized CC bond length data, a critical phenomenon couldn’t be ignored. As illustrated in Fig.2, the length between double bonds with non-methylated groups (C7 = C8 1.351 Å, C11 = C12 1.362 Å, C15=C15′ 1.366 Å) is shorter than the methyl bonds (C5 = C6 1.354 Å, C9 = C10 1.366 Å, C13 = C14 1.371 Å) respectively. However, the length between single bond with methyl group C12-C13 1.442 Å is longer than non-methylated bond C10-C11 1.433 Å. This phenomenon is not consistent with 192
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Fig. 1. a The drawing of β-Car with the numbered carbon atoms. The molecule is characterized by 1,2,…15 and 1′, 2′,…15′ from the beginning of each head group. b Optimized geometry of β-Car using DFT B3LYP/6–311 G basis set. Table 1 The compared optimized lengths of CC bonds using B3LYP/6–31 G and 6–311 G (d,p) basis sets which represent well matching value.
a
R abond
6-31G
6-311G (d, p)
C(5)=C(6) C(6)—C(7) C(7)=C(8) C(8)—C(9) C(9) =C(10) C(10)—C(11) C(11)=C(12) C(12)—C(13) C(13)=C(14) C(14)—C(15) C(15)=C(15') C(14')—C(15') C(13')=C(14') C(12')—C(13') C(11')=C(12') C(10')—C(11') C(9')=C(10') C(8')—C(9') C(7')=C(8') C(6')—C(7') C(5')=C(6')
1.363 1.476 1.359 1.457 1.373 1.436 1.369 1.445 1.378 1.430 1.373 1.430 1.378 1.445 1.369 1.436 1.373 1.457 1.359 1.476 1.363
1.354 1.475 1.351 1.453 1.366 1.433 1.362 1.442 1.371 1.427 1.366 1.427 1.371 1.442 1.362 1.433 1.366 1.453 1.351 1.475 1.354
Figure 1a, β-Car.
the basis conception of π-electron delocalization. For double bond, the length of center bond is longer than the margin part. But for single bond, it displays opposite character. Our data reveals β-Car molecule shows a hyper-conjugation effect. Several researches also testified the methyl groups could generate the hyper-conjugation effect that induce π-electron delocalization extend along the conjugated chain [20–22]. Moreover, the π-electron delocalization and effective conjugation degree have close relationship with BLA parameter. To some degree, conjugation degree and BLA are in inverse proportion in a conjugated system. Meanwhile, it can be clearly seen from Fig. 3 that the electrons move along the middle of the β-Car chain. Combined BLA with molecular orbital analysis, the β-ring groups connected with double bond numbered 6,7 and 6′, 7′ at each end of the chain, unavoidably will work to the vibrational properties of β-Car. The β rings are easy rotated and the structure will be strong influenced during phase transition. The extent of π-electron delocalization when β rings with no rotation (0°) is much bigger than that of the perpendicular form (90°) already been shown in previous research work [23]. Because the cooling process causes a phase change in the solution, the β ring’s rotation will further modulate its molecular structure.
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Fig. 2. CC bond length optimized by B3LYP/6–311 G basis set shows BLA apparent rises at the tail of the chain, while it displays an decreasing trend in the center of the chain.
Fig. 3. Electrons move along the middle of the β-Car chain from the highest occupied molecular orbital (HOMO) schematic illustration.
3.2. Electronic energy of 0-0 peak diminishes with the decreasing temperature Absorption spectra of β-Car at temperature range from 354 K to 298 K are shown in Fig.4. From comprehensive studies on polyene system, the ground singlet state (S0 or 11Ag−), first excited singlet state (S1 or 21Ag−) and second excited singlet state (S2 or 11Bu−) are three electronic states acquired in the absorption spectra [24,25]. The transition from S0 to S1 is forbidden because of the C2h symmetry principle, but transition from S0 to S2 is permitted generated from the HOMO→LUMO transition [26]. Three vibronic bands characterized by 0-0, 0–1, 0–2 from S0 to S2 transition compose the main absorption of β-Car [7,15,27–30]. The electronic energy of 0-0 peak from S0 to S2 transition presents a diminishing trend with the decreasing temperature is shown in Fig.5. Numerous studies have been given to the impact of temperature on the electronic energy of 0-0 peak from S0 to S2 transition for
Fig. 4. Electronic absorption spectra red shift for β-Car in DMSO with decreasing temperature (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article). 194
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Fig. 5. The electronic energy of 0-0 peak from S0 to S2 transition represents a diminishing trend with the decreasing temperature in β-Car.
carotenoids [6,7,15,27–29,31]. Dispersive force is deduced to take the response to induce the electronic energy change. Effective conjugation length model is another factor which can tune the electronic structure at the condition of changing temperature. The palpable prolonged conjugation length with diminishing temperature could be described using following description [32]. n(T ) = n 0 eˆ(ε /kT ) , where n 0 is the effective conjugation length at high temperatures, ε is the characteristic energy and k is Boltzmann constant. Moreover, according to the NBO theory, π-π* orbital interactions strengthen π-conjugation efficiency that lead the π-electron freefloat longer to the end of the chain [9]. LUMO−HOMO energy gap decreases with the increasing effective conjugation length which finally brings about the 0-0 electronic energy declines with diminishing temperature. The resonance effect is improved due to the absorption band red shift analyzed using the effective conjugation length and π-electron delocalization model. It will be further proved by following observed evolution of the molecular Raman properties. 3.3. Temperature influence on Raman scattering cross section (RSCS) Raman spectra of β-Car dissolved in DMSO of 10−6 concentration at different temperatures are illustrated in Fig.6. β-Car exhibits two characteristic resonance Raman lines 1520 cm-1 v1 mode and 1155 cm-1 v2 mode. They are denoted CC double bond and single bond stretching vibration [2]. The intensity of internal standard 992 cm-1 Raman line of benzene is characterized by * to be used in the calculation. The RSCS of β-Car in DMSO can be acquired using EqS. (1) and (2) [33,34].
I v (v − v R )3 ⎤ ⎛ CR ⎞ σS = σR ·⎛ s ⎞ ⎡ 0 0 L (v0) 3 ⎢ I R ⎝ ⎠ ⎣ v0 (v0 − vS ) ⎥ ⎦ ⎝ CS ⎠ ⎜
⎟
⎜
n2 + 2 ⎞ L (v0) = ⎛ ⎝ 3 ⎠ ⎜
⎟
(1)
4
⎟
(2)
Where σS is RSCS of β-Car, σR is RSCS of benzene which is a constant value. Is represents the Raman intensity of 1520 cm−1 or 1155 cm−1 and IR is Raman intensity of 992 cm−1 band of benzene. The wavenumber v0 , v R , vS are from incident excitation beam, 992 cm−1 band of benzene and band of β-Car, respectively. CR is the molar concentration ratio of benzene relative to β-Car. L (v0 ) is CS
Fig. 6. Raman Spectroscopy of β-Car in DMSO at different temperatures at concentration 10−6. 195
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Fig. 7. Temperature influence on the RSCS of β-Car in DMSO (a) CC double bond (C]C) (b) CC single bond (CeC). RSCS sharply decreases during phase transition from 293 K to 283 K (from B to C).
the local field correction factor according to Onsager’s theory. n is the solvent refractive index. The influence of reflect index can be over looked because of the severely low concentration of benzene. Fig.7 indicates the RSCS of double bond ν1 and single bond ν2 modes describe much the same temperature dependences. The blatant increase of the RSCS before 293 K (from point A to B) signifies the powerful relationship between β-rings and β-Car chain. Decreasing temperature induces liquid density present a rising trend and the intermolecular distance between molecules diminishes. These phenomenon changes the induced dipole stronger and the absorption red shift for β-Car. These combined factors result in a reinforced resonance effect. The increasing trend for intensity ratio of C]C to CeC with decreasing temperature can further prove the resonance intensification shown in Fig.8. Moreover, based on the vibration theory, the Raman intensity is summed up by the Raman active of contrary vibration direction of CC bond stretching. With the decreasing temperature, thermal disorder follows a diminishing trend then to constrain the CC bond vibrating around the flat surface of the chain, therefore makes for amplified conjugation degree. Free floating π-conjugated electron to longer distance makes π-electron delocalization extend. The conjoint CC vibrations integrate more planar and highly ordered properties according to nonlinear coherent model [35–38]. These factors result in a rising RSCS from section A to B. An obvious trend is that RSCS sharply decreases during 293 K to 283 K (from B to C) which is corresponding to DMSO freezing point. The liquid sample gradually freeze to solid status during the liquid-solid phase transition. The obvious dropping RSCS of CC single and double bond origins from the reduced conjugation degree and π electron delocalization. The configuration of β-Car recombine and new atom position displace the formal one with this complicated environment. Base on DFT calculation in previous section that the largest BLA value at the end of the chain. We can further infer the incidental β ring will be rotated when suffering with large field energy. Liu(etc.) illustrated the dwindling of π-electron delocalization as the β ring is twisted from 0° to 90° because of the clutter [23]. Vibrational frequency of the CC single and doule bond modes depend resolutely on shift degree of equilibrium position. When the mutual vibration contains the in-phase distortion along the chain, the impact from single bond will quash the double bonds, therefore resulting in a frail Raman intensity [20]. So the rapid downward trend for RSCS will happen during the phase transition. With constant decreasing temperature, β-Car absolutely exists in solid state and crystallization occurs after phase transition finished. β ring will be rotated to in plane vibration step by step amplify the conjugation length. Strong structure order induces RSCS increases steadily (from C to D).
Fig. 8. The ratio of relative intensity of Iν1 to Iν2 increases with decreasing temperature. 196
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Fig. 9. The FWHM of C]C bond of β-Car drops 5 cm−1 when temperature decrease from 333 K to 263 K.
The spectral bandwidth was also tested for representative Raman bands. The most conspicuous temperature dependence of spectral width is found in DMSO solution for the v1 band. As shown in Fig.9, the full-width at half-maximum (FWHM) of the CC double bond stretching mode decreases 5 cm−1 from ambient temperature to 328 K. The inhomogeneous width diminishes rapidly with decreasing temperature for the whole temperature range. On the other hand, the modulation amplitude evenly decreases with temperature. 4. Conclusions The outcome of phase-transition on the geometry and Raman spectra of β-Car have been typified through DFT analysis. The configurational contortions of β-Car brought about by rotated β-rings resulted in a sharp decrease during phase transition. It is good evidence that DFT calculations provide a meaningful investigation on molecular Raman properties during phase transition. The intricate analysis on Raman and absorption spectra offer a patent perception on the molecule structure. The whole discussions generate a resolute impact on temperature for modulate the structure of β-Car in solution. This work is expected to be beneficial information to modulate the photoelectric material at varying temperature conditions. Declaration of interest None Acknowledgments This work was supported by the National Natural Science Foundation of China [grant number 41404109] and the Science and Technology Development Project of Jilin Province [grant number 20190303108SF]. The authors gratefully thank Dr. Xiao-Qiang Di for the generous use of Gaussian 09 software in this work. References [1] M.M. Mendes-Pinto, E. Sansiaume, H. Hashimoto, B. Robert, Electronic absorption and ground state structure of carotenoid molecules, J. Phys. Chem. B 117 (2013) 11015–11021, https://doi.org/10.1023/A:1014715114520. [2] C. Uragami, K. Saito, M. Yoshizawa, P. Molnár, H. Hashimoto, Unified analysis of optical absorption spectra of carotenoids based on a stochastic model, Arch. Biochem. Biophys. 650 (2018) 49–58, https://doi.org/10.1016/j.abb.2018.04.021. [3] N.J. Fraser, H. Hashimoto, R.J. Cogdell, Carotenoids and bacterial photosynthesis: the story so far…, Photosynth. Res. 70 (2001) 249–256, https://doi.org/10. 1023/A:1014715114520. [4] T. Polívka, V. Sundström, Ultrafast dynamics of carotenoid excited states-from solution to natural and artificial systems, Chem. Rev. 104 (4) (2004) 2021–2071, https://doi.org/10.1021/cr020674n. [5] T. Polívka, H.A. Frank, Molecular factors controlling photosynthetic light harvesting by carotenoids, Acc. Chem. Res. 43 (8) (2010) 1125–1134, https://doi.org/ 10.1021/ar100030m. [6] M. Macernis, D. Galzerano, J. Sulskus, E. Kish, Y.H. Kim, S. Koo, L. Valkunas, B. Robert, Resonance Raman spectra of carotenoid molecules: influence of methyl substitutions, J. Phys. Chem. A 119 (1) (2014) 56–66, https://doi.org/10.1021/jp510426m. [7] M. Macernis, J. Sulskus, S. Malickaja, B. Robert, L. Valkunas, Resonance Raman spectra and electronic transitions in carotenoids: a density functional theory study, J. Phys. Chem. A 118 (10) (2014) 1817–1825, https://doi.org/10.1021/jp406449c. [8] D. Gosztola, M.R. Wasielewski, Resonance Raman spectroscopy of a chlorophyll-porphyrin heterodimer: excitation profile in the 400-450-nm region, J. Phys. Chem. 97 (1993) 9599–9602, https://doi.org/10.1021/j100140a012. [9] M. Bruschi, P.A. Limacher, J. Hutter, H.P. Lüthi, A scheme for the evaluation of Electron delocalization and conjugation efficiency in linearly π-Conjugated systems, J. Chem. Theory Comput. 5 (3) (2009) 506–514, https://doi.org/10.1021/ct8004358. [10] Y.F. Wang, Z.Y. Yu, J. Wu, C.B. Liu, Electron delocalization and charge transfer in polypeptide chains, J. Phys. Chem. A 113 (39) (2009) 10521–10526, https:// doi.org/10.1021/jp9020036.
197
Optik - International Journal for Light and Electron Optics 185 (2019) 191–198
G. Qu, et al.
[11] T. Noguchi, H. Hayashi, M. Tasumi, G.H. Atkinson, Solvent effects on the ag C=C Stretching Mode in the 21Ag− Excited State of β-Carotene and Two Derivatives: Picosecond Time-Resolved Resonance Raman Spectroscopy, J. Phys. Chem. 95 (8) (1991) 3167–3172, https://doi.org/10.1002/chin.199131048. [12] W.L. Liu, Z.R. Zheng, R.B. Zhu, Z.G. Liu, D.P. Xu, H.M. Yu, W.Z. Wu, A.H. Li, Y.Q. Yang, W.H. Su, Effect of pressure and solvent on Raman spectra of all-trans-βcarotene, J. Phys. Chem. A 111 (40) (2007) 10044–10049, https://doi.org/10.1021/jp074048b. [13] N. Gong, H.Y. Fu, S.H. Wang, X.W. Cao, Z.W. Li, C.L. Sun, Z.W. Men, All-trans-β-carotene absorption shift and electron-phonon coupling modulated by solvent polarizability, J. Mol. Liq. 251 (2018) 417–422, https://doi.org/10.1016/j.molliq.2017.12.096. [14] E.J.G. Peterman, T. Pullerits, R. van Grondelle, H. van Amerongen, Electron−phonon coupling and vibronic fine structure of light-harvesting complex II of green plants: temperature dependent absorption and high-resolution fluorescence spectroscopy, J. Phys. Chem. B 101 (22) (1997) 4448–4457, https://doi.org/10. 1021/jp962338e. [15] H. Torii, M. Tasumi, Vibrational structure and temperature dependence of the electronic absorption (11Bu⟵11Ag) of all-trans-β-carotene, J. Phys. Chem. 94 (1) (1990) 227–231, https://doi.org/10.1021/j100364a037. [16] J.A. Burt, X.H. Zhao, J.L. McHale, Inertial solvent dynamics and the analysis of spectral line shapes: Temperature-dependent absorption spectrum of β-carotene in nonpolar solvent, J. Chem. Phys. 120 (9) (2004) 4344–4354, https://doi.org/10.1063/1.1644534. [17] T.Y. Liu, S.N. Xu, Z.W. Li, M.Z. Wang, C.L. Sun, Temperature induced changes in resonance Raman spectra intensity of all-trans-β-carotene: changes in the fundamental, combination and overtone modes, Spectrochim. Acta A Mol. Biomol. Spectrosc. 131 (15) (2014) 153–157, https://doi.org/10.1016/j.saa.2014.04. 069. [18] S. Li, Z.L. Li, S.H. Wang, S.Q. Gao, C.L. Sun, Z.W. Li, The electron–phonon coupling of fundamental, overtone, and combination modes and its effects on the resonance Raman spectra, Mater. Res. Bull. 72 (2015) 1–6, https://doi.org/10.1016/j.materresbull.2015.07.006. [19] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford CT, 2009. [20] C. Castiglioni, M. Tommasini, G. Zerbi, Raman spectroscopy of polyconjugated molecules and materials confinement effect in one and two dimensions, Phil. Trans. R. Soc. Lond. A 362 (2004) 2425–2459, https://doi.org/10.1098/rsta.2004.1448. [21] M.O. Senge, H. Hope, K.M. Smith, Structure and Conformation of Photosynthetic Pigments and Related Compounds 3. Crystal Structure ofβ-Carotene, Z. Naturforsch. C 47 (5-6) (1992) 474–476, https://doi.org/10.1515/znc-1992-0623. [22] S. Schlücker, A. Szeghalmi, M. Schmitt, J. Popp, W. Kiefer, Density functional and vibrational spectroscopic analysis of β‐carotene, J. Raman Spectrosc. 34 (2003) 413–419, https://doi.org/10.1002/jrs.1013. [23] W.L. Liu, Z.G. Wang, Z.R. Zheng, A.H. Li, W.H. Su, Effect of β-ring rotation on the structures and vibrational spectra of β carotene density functional theory analysis, J. Phys. Chem. A 112 (42) (2008) 10580–10585, https://doi.org/10.1021/jp802024v. [24] R.J. Cogdell, H.A. Frank, How carotenoids function in photosynthetic bacteria, B.B.A. Biomembranes 895 (1987) 63–79, https://doi.org/10.1016/S03044173(87)80008-3. [25] H.A. Frank, A.J. Young, G. Britton, R.J. Cogdell, The photochemistry of carotenoids, in: J.Amesz Govindjee, E.M. Aro, J. Barber, R.E. Blankenship, N. Murata, D.R. Ort (Eds.), Carorenoids in Photosynthesis, Kluwer Academic publishers, London, 1992, pp. 137–157. [26] H.A. Frank, R. Frahoosh, M.L. Aldema, B. Decoster, R.L. Christensen, R. Gebhard, J. Lugtenburg, Carotenoid-to-bacteriochlorophyll singlet energy transfer in carotenoid-incorporated B850 light-harvesting complexes of rhodobacter sphaeroides R-26.1, Photochem. Photobiol. 57 (1) (1993) 49–55, https://doi.org/10. 1111/j.1751-1097.1993.tb02254.x. [27] L. Fiedor, J. Heriyanto, M. Fiedor, Pilch, Effects of molecular symmetry on the electronic transitions in carotenoids, J. Phys. Chem. Lett. 7 (10) (2016) 1821–1829, https://doi.org/10.1021/acs.jpclett.6b00637. [28] S.L. Bondarev, S.M. Bachilo, S.S. Dvornikov, S.A. Tikhomirov, S2→S0 fluorescence and transient Sn ⟵ S1 absorption of all-trans-β-carotene in solid and liquid solutions, J. Photochem. Photobio. A 46 (3) (1989) 315–322, https://doi.org/10.1016/1010-6030(89)87048-0. [29] R.J. Thrash, H.L.B. Fang, G.E. Leroi, The Raman excitation profile spectrum of β-carotene in the preresonance region: evidence for a low-lying singlet state, J. Chem. Phys. 67 (12) (1977) 5930–5933, https://doi.org/10.1063/1.434800. [30] A. Dreuw, P.H.P. Harbach, J.M. Mewes, M. Wormit, Quantum chemical excited state calculations on pigment–protein complexes require thorough geometry reoptimization of experimental crystal structures, Theor. Chem. Acc. 125 (2010) 419–426, https://doi.org/10.1007/s00214-009-0680-3. [31] M.M. Mendes-Pinto, E. Sansiaume, H. Hashimoto, A.A. Pascal, A. Gall, B. Robert, Electronic absorption and ground state structure of carotenoid molecules, J. Phys. Chem. B 117 (38) (2013) 11015–11021, https://doi.org/10.1021/jp309908r. [32] W.R. Salaneck, O. Inganäs, B. Thémans, J.O. Nilson, B. Sjögren, J.E. Osterholm, J.L. Brédas, S. Svensson, Thermochromism in poly(3hexylthiophene) in the solid state: a spectroscopic study of temperature dependent conformational defects, J. Chem. Phys. 89 (8) (1988) 4613–4619, https://doi.org/10.1063/1.454802. [33] J.M. Dudik, C.R. Johnson, S.A. Asher, Wavelength dependence of the preresonance Raman cross sections of CH3CN, SO42−, ClO4−, and NO3−, J. Chem. Phys. 82 (4) (1985) 1732–1740, https://doi.org/10.1063/1.448405. [34] N. Biswas, S. Umapathy, Simple approach to determining absolute Raman cross sections using an optical parametric oscillator, Appl.Spectrosc. 52 (4) (1998) 496–499, https://doi.org/10.1366/0003702981944021. [35] D.Yu. Paraschuk, V.M. Kobryanskii, Coherent electron-lattice vibrations in trans-nanopolyacetylene probed by raman scattering, Phys.Rev.L 87 (20) (2001) 207402, https://doi.org/10.1103/PhysRevLett.87.207402 (1-4). [36] G. Orlandi, F. Zerbetto, M.Z. Zgierski, Theoretical analysis of spectra of short polyenes, Chem. Rev. 91 (5) (1991) 867–891, https://doi.org/10.1021/ cr00005a012. [37] B. Kirtman, C.E. Dykstra, B. Champagne, Major intermolecular effects on nonlinear electrical response in a hexatriene model of solid state polyacetylene, Chem. Phys. Lett. 305 (1999) 132–138, https://doi.org/10.1016/S0009-2614(99)00375-9. [38] D.Yu. Paraschuk, V.M. Kobryanskii, Synchronous Electron–Nuclear vibrations in a π-Conjugated nanopoly(acetylene) chain, JETP Lett. 73 (2001) 170–174, https://doi.org/10.1134/1.1364545.
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Resonance Raman features all-trans-β-carotene during phase transition and theoretical investigation analysis
T
Guannan Qua,c, Minsi Xina, Qiang Jiaa, Pengcheng Caia, Guangyong Jinb, Yunquan Zhoua, Chunyu Liua, Yong Tana, Ye Zhanga, Zhihai Yaoa, Aoran Fenga, ⁎ Hongxing Caia,c, a
School of Science, Changchun University of Science and Technology, Changchun, 130022, China Jilin Key Laboratory of Solid-State Laser Technology and Application, Changchun University of Science and Technology, Changchun, 130022, China c Key laboratory of Jilin Province for Spectral Detection Science and Technology, Changchun University of Science and Technology, Changchun, 130022, China b
A R T IC LE I N F O
ABS TRA CT
Keywords: All-trans-β-carotene Density functional theory Phase transition Raman scattering cross section
Raman and absorption features all-trans-β-carotene (β-Car) liquefied in dimethyl sulfoxide (DMSO) of 10−6 concentration at temperature range from 333K to 263K are recorded. The usage of density functional theory (DFT) calculations could meticulously anticipate the molecular vibration mechanism. The calculation of CC bond length alternation (BLA) and graphic illustration of the highest occupied molecular orbital (HOMO) of β-Car can help decipher the vibration mechanism during phase transition. The Raman scattering cross section (RSCS) of the CC single and double bonds roughly increases when temperature decreases during pure liquid- solid phase condition due to extended effective conjugation length (ECL). The RSCS sharply drops during the phase transition because the β rings are very likely rotated from 0° to 90°. Electronic transition energy (0-0) of absorption spectra declining lead to the amplified resonance effect. This research is counted upon to be valuable by using DFT calculations to investigate the influence of phase transition on resonance Raman character of β-Car.
1. Introduction Carotenoids are treated as organic biomolecules which act a pivotal part in biology photosynthesis [1]. Their singlet and triplet type energy transfer manner plays a vital role in light reaction, exposure and harvesting [1,2]. β-Car is a conjugated molecule built from 11 alternative single and double bond units. Its π electron delocalization is protracted into the β rings which is located at the end of the chain and is always regarded as a referential model in biophysics and biochemistry filed. Carotenoids could carry out structural counterpoise in light-harvesting due to the assembly of pigment-protein complexes [3]. Their linear conjugated polyene structure makes it possible to accomplish the energy transfer in singlet and excited states [2,4,5]. Comprehensive researches showed crux in surmising the entire electronic structure of β-car [6]. Copious representations of resonance Raman and absorption spectra of β-Car have already been developed [1,7]. The optical features of carotenoids could be powerfully affected by ECL [7]. Resonance Raman spectra provide the support on better apprehending the relationship between the structure and the electronic states of the polyene in photosynthetic process [8]. Natural bond orbital (NBO) theory could be applied to supervise the evolvement of electron delocalization. The comparably feeble orbital ⁎
Corresponding author at: School of Science, Changchun University of Science and Technology, Changchun, 130022, China. E-mail address: [email protected] (H. Cai).
https://doi.org/10.1016/j.ijleo.2019.03.109 Received 2 February 2019; Accepted 19 March 2019 0030-4026/ © 2019 Elsevier GmbH. All rights reserved.
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interactions led to the reduction of conjugation efficacy for the polyeneynes [9,10]. Conformational fluctuations of β-Car induced by solvent effect can largely sway the bandwidth properties [11]. Some investigations on carotenoid optical response influenced by external field have already been implemented. Raman and absorption properties of polyenes changed a lot with different pressure and solvent effects [12,13]. Moreover, the multitudinous temperature dependent Raman and absorption profiles of β-Car reveal the important phenomenon [14–16]. However, the analysis is mostly fixated on the frequency alteration in various situation but pay less attention to Raman intensity. In addition, Raman intensity properties of β-Car on the condition of phase transition induced by temperature is still limited. Some Raman explorations on β-Car manifest that the electron-phonon coupling combined with coherent weakly damped electron lattice vibrations had large efforts to Raman intensity [17,18]. Parameter variations caused by the environment induce Raman intensity changed during phase transition are still largely unknown. To further dig out the micro-phenomenon, quantum chemistry calculations are utilized to further interpret these observations. In our research, the absorption and Raman properties of β-Car molecule in DMSO at temperature range from 333 K to 263 K have been scrutinized. The intensity of Raman spectra and electronic energy of absorption gives information that the effective conjugation length and π electron delocalization will straightforwardly influence the vibration character. DFT calculations, using the B3LYP functional and theoretical investigation helps analyze the molecular structure. CC bond at each end of the chain could be easily revolved during intricate environment. This work provides an idea for modulating temperature to change Raman intensity of carotenoid. It can also provide favorable information on molecular structure during phase transition through theoretical calculation. 2. Materials and methods 2.1. All-trans-β-carotene preperation β-Car (purity is ≥97.0%, C40H56) tested in this research was got from Sigma-Aldrich (St. Louis, MO). It should be stored at negative 20 ° in the lightless room and with no further purification. 2.2. Solvents preperation The β-Car was dissolved in DMSO (C2H6SO AR, 99.8%) and benzene (C6H6 anhydrous, analytical grade 99.5%) at a concentration of 2.1 × 10−6 M. The experiment should be carried out at once to prevent the solution further degradation. The 992 cm-1 line of benzene at a concentration of ˜10−7M was used as internal standard. 2.3. Raman and absorption spectroscopy The absorption spectra were explored using Agilent Technologies UV–vis-NIR Spectrophotometer (Cary-5000). The solution was injected in an enclosed quartz cuvette with 1 cm × 1 cm square. Raman spectra were acquired by a three-stage monochromator (Trivista 555 CRS, USA). A 5 mW Ar + laser with 532 nm wavelength was supplied the excitations and recorded in a nitrogen-flow cryostat. A back-illuminated CCD detector(Princeton Instruments Pylon 400)with 90° signal acquiring was installed with the whole equipment. The sample status was monitored through a 20 times objective lens with 0.12 numerical aperture. The scanning speed for absorption and Raman spectra are 1 nm step and 10cm−1/min, respectively. All the experiments were conducted in a dark room. 2.4. Computational approach The calculations of structure and vibrational spectroscopic characteristics were performed for β-car using the DFT approaches executed in the Gaussian09 series of programs [19]. The usage of B3LYP density functional combine with 6–31 G and 6–311 G (d,p) basis sets had a great contribution in this study. 3. Experiment results and discussion 3.1. DFT calculation about the β-Car structure The schematic and optimized geometry of the β-Car molecule obtained through B3LYP/6–311 G basis set is illustrated in Fig.1a and Fig.1b. The numbered carbon atoms are marked along the chain. The pattern of the chain is consist of 11 alternated single and double CC bonds with two β rings. The optimized lengths of CC bonds using B3LYP/6–31 G and 6–311 G (d,p) basis sets listed in Table1 represent well matching value. The deviation of length between single and double bond which is named as BLA optimized by B3LYP/6–311 G basis set show apparent rise at the tail of the chain, while it displays an decreasing trend in the center part (Fig.2). The larger BLA at end of the chain indicates that the bonds of incidental part of polyene chain is more unpredictable than the bonds at the center. To further dig out the optimized CC bond length data, a critical phenomenon couldn’t be ignored. As illustrated in Fig.2, the length between double bonds with non-methylated groups (C7 = C8 1.351 Å, C11 = C12 1.362 Å, C15=C15′ 1.366 Å) is shorter than the methyl bonds (C5 = C6 1.354 Å, C9 = C10 1.366 Å, C13 = C14 1.371 Å) respectively. However, the length between single bond with methyl group C12-C13 1.442 Å is longer than non-methylated bond C10-C11 1.433 Å. This phenomenon is not consistent with 192
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Fig. 1. a The drawing of β-Car with the numbered carbon atoms. The molecule is characterized by 1,2,…15 and 1′, 2′,…15′ from the beginning of each head group. b Optimized geometry of β-Car using DFT B3LYP/6–311 G basis set. Table 1 The compared optimized lengths of CC bonds using B3LYP/6–31 G and 6–311 G (d,p) basis sets which represent well matching value.
a
R abond
6-31G
6-311G (d, p)
C(5)=C(6) C(6)—C(7) C(7)=C(8) C(8)—C(9) C(9) =C(10) C(10)—C(11) C(11)=C(12) C(12)—C(13) C(13)=C(14) C(14)—C(15) C(15)=C(15') C(14')—C(15') C(13')=C(14') C(12')—C(13') C(11')=C(12') C(10')—C(11') C(9')=C(10') C(8')—C(9') C(7')=C(8') C(6')—C(7') C(5')=C(6')
1.363 1.476 1.359 1.457 1.373 1.436 1.369 1.445 1.378 1.430 1.373 1.430 1.378 1.445 1.369 1.436 1.373 1.457 1.359 1.476 1.363
1.354 1.475 1.351 1.453 1.366 1.433 1.362 1.442 1.371 1.427 1.366 1.427 1.371 1.442 1.362 1.433 1.366 1.453 1.351 1.475 1.354
Figure 1a, β-Car.
the basis conception of π-electron delocalization. For double bond, the length of center bond is longer than the margin part. But for single bond, it displays opposite character. Our data reveals β-Car molecule shows a hyper-conjugation effect. Several researches also testified the methyl groups could generate the hyper-conjugation effect that induce π-electron delocalization extend along the conjugated chain [20–22]. Moreover, the π-electron delocalization and effective conjugation degree have close relationship with BLA parameter. To some degree, conjugation degree and BLA are in inverse proportion in a conjugated system. Meanwhile, it can be clearly seen from Fig. 3 that the electrons move along the middle of the β-Car chain. Combined BLA with molecular orbital analysis, the β-ring groups connected with double bond numbered 6,7 and 6′, 7′ at each end of the chain, unavoidably will work to the vibrational properties of β-Car. The β rings are easy rotated and the structure will be strong influenced during phase transition. The extent of π-electron delocalization when β rings with no rotation (0°) is much bigger than that of the perpendicular form (90°) already been shown in previous research work [23]. Because the cooling process causes a phase change in the solution, the β ring’s rotation will further modulate its molecular structure.
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Fig. 2. CC bond length optimized by B3LYP/6–311 G basis set shows BLA apparent rises at the tail of the chain, while it displays an decreasing trend in the center of the chain.
Fig. 3. Electrons move along the middle of the β-Car chain from the highest occupied molecular orbital (HOMO) schematic illustration.
3.2. Electronic energy of 0-0 peak diminishes with the decreasing temperature Absorption spectra of β-Car at temperature range from 354 K to 298 K are shown in Fig.4. From comprehensive studies on polyene system, the ground singlet state (S0 or 11Ag−), first excited singlet state (S1 or 21Ag−) and second excited singlet state (S2 or 11Bu−) are three electronic states acquired in the absorption spectra [24,25]. The transition from S0 to S1 is forbidden because of the C2h symmetry principle, but transition from S0 to S2 is permitted generated from the HOMO→LUMO transition [26]. Three vibronic bands characterized by 0-0, 0–1, 0–2 from S0 to S2 transition compose the main absorption of β-Car [7,15,27–30]. The electronic energy of 0-0 peak from S0 to S2 transition presents a diminishing trend with the decreasing temperature is shown in Fig.5. Numerous studies have been given to the impact of temperature on the electronic energy of 0-0 peak from S0 to S2 transition for
Fig. 4. Electronic absorption spectra red shift for β-Car in DMSO with decreasing temperature (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article). 194
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Fig. 5. The electronic energy of 0-0 peak from S0 to S2 transition represents a diminishing trend with the decreasing temperature in β-Car.
carotenoids [6,7,15,27–29,31]. Dispersive force is deduced to take the response to induce the electronic energy change. Effective conjugation length model is another factor which can tune the electronic structure at the condition of changing temperature. The palpable prolonged conjugation length with diminishing temperature could be described using following description [32]. n(T ) = n 0 eˆ(ε /kT ) , where n 0 is the effective conjugation length at high temperatures, ε is the characteristic energy and k is Boltzmann constant. Moreover, according to the NBO theory, π-π* orbital interactions strengthen π-conjugation efficiency that lead the π-electron freefloat longer to the end of the chain [9]. LUMO−HOMO energy gap decreases with the increasing effective conjugation length which finally brings about the 0-0 electronic energy declines with diminishing temperature. The resonance effect is improved due to the absorption band red shift analyzed using the effective conjugation length and π-electron delocalization model. It will be further proved by following observed evolution of the molecular Raman properties. 3.3. Temperature influence on Raman scattering cross section (RSCS) Raman spectra of β-Car dissolved in DMSO of 10−6 concentration at different temperatures are illustrated in Fig.6. β-Car exhibits two characteristic resonance Raman lines 1520 cm-1 v1 mode and 1155 cm-1 v2 mode. They are denoted CC double bond and single bond stretching vibration [2]. The intensity of internal standard 992 cm-1 Raman line of benzene is characterized by * to be used in the calculation. The RSCS of β-Car in DMSO can be acquired using EqS. (1) and (2) [33,34].
I v (v − v R )3 ⎤ ⎛ CR ⎞ σS = σR ·⎛ s ⎞ ⎡ 0 0 L (v0) 3 ⎢ I R ⎝ ⎠ ⎣ v0 (v0 − vS ) ⎥ ⎦ ⎝ CS ⎠ ⎜
⎟
⎜
n2 + 2 ⎞ L (v0) = ⎛ ⎝ 3 ⎠ ⎜
⎟
(1)
4
⎟
(2)
Where σS is RSCS of β-Car, σR is RSCS of benzene which is a constant value. Is represents the Raman intensity of 1520 cm−1 or 1155 cm−1 and IR is Raman intensity of 992 cm−1 band of benzene. The wavenumber v0 , v R , vS are from incident excitation beam, 992 cm−1 band of benzene and band of β-Car, respectively. CR is the molar concentration ratio of benzene relative to β-Car. L (v0 ) is CS
Fig. 6. Raman Spectroscopy of β-Car in DMSO at different temperatures at concentration 10−6. 195
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Fig. 7. Temperature influence on the RSCS of β-Car in DMSO (a) CC double bond (C]C) (b) CC single bond (CeC). RSCS sharply decreases during phase transition from 293 K to 283 K (from B to C).
the local field correction factor according to Onsager’s theory. n is the solvent refractive index. The influence of reflect index can be over looked because of the severely low concentration of benzene. Fig.7 indicates the RSCS of double bond ν1 and single bond ν2 modes describe much the same temperature dependences. The blatant increase of the RSCS before 293 K (from point A to B) signifies the powerful relationship between β-rings and β-Car chain. Decreasing temperature induces liquid density present a rising trend and the intermolecular distance between molecules diminishes. These phenomenon changes the induced dipole stronger and the absorption red shift for β-Car. These combined factors result in a reinforced resonance effect. The increasing trend for intensity ratio of C]C to CeC with decreasing temperature can further prove the resonance intensification shown in Fig.8. Moreover, based on the vibration theory, the Raman intensity is summed up by the Raman active of contrary vibration direction of CC bond stretching. With the decreasing temperature, thermal disorder follows a diminishing trend then to constrain the CC bond vibrating around the flat surface of the chain, therefore makes for amplified conjugation degree. Free floating π-conjugated electron to longer distance makes π-electron delocalization extend. The conjoint CC vibrations integrate more planar and highly ordered properties according to nonlinear coherent model [35–38]. These factors result in a rising RSCS from section A to B. An obvious trend is that RSCS sharply decreases during 293 K to 283 K (from B to C) which is corresponding to DMSO freezing point. The liquid sample gradually freeze to solid status during the liquid-solid phase transition. The obvious dropping RSCS of CC single and double bond origins from the reduced conjugation degree and π electron delocalization. The configuration of β-Car recombine and new atom position displace the formal one with this complicated environment. Base on DFT calculation in previous section that the largest BLA value at the end of the chain. We can further infer the incidental β ring will be rotated when suffering with large field energy. Liu(etc.) illustrated the dwindling of π-electron delocalization as the β ring is twisted from 0° to 90° because of the clutter [23]. Vibrational frequency of the CC single and doule bond modes depend resolutely on shift degree of equilibrium position. When the mutual vibration contains the in-phase distortion along the chain, the impact from single bond will quash the double bonds, therefore resulting in a frail Raman intensity [20]. So the rapid downward trend for RSCS will happen during the phase transition. With constant decreasing temperature, β-Car absolutely exists in solid state and crystallization occurs after phase transition finished. β ring will be rotated to in plane vibration step by step amplify the conjugation length. Strong structure order induces RSCS increases steadily (from C to D).
Fig. 8. The ratio of relative intensity of Iν1 to Iν2 increases with decreasing temperature. 196
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Fig. 9. The FWHM of C]C bond of β-Car drops 5 cm−1 when temperature decrease from 333 K to 263 K.
The spectral bandwidth was also tested for representative Raman bands. The most conspicuous temperature dependence of spectral width is found in DMSO solution for the v1 band. As shown in Fig.9, the full-width at half-maximum (FWHM) of the CC double bond stretching mode decreases 5 cm−1 from ambient temperature to 328 K. The inhomogeneous width diminishes rapidly with decreasing temperature for the whole temperature range. On the other hand, the modulation amplitude evenly decreases with temperature. 4. Conclusions The outcome of phase-transition on the geometry and Raman spectra of β-Car have been typified through DFT analysis. The configurational contortions of β-Car brought about by rotated β-rings resulted in a sharp decrease during phase transition. It is good evidence that DFT calculations provide a meaningful investigation on molecular Raman properties during phase transition. The intricate analysis on Raman and absorption spectra offer a patent perception on the molecule structure. The whole discussions generate a resolute impact on temperature for modulate the structure of β-Car in solution. This work is expected to be beneficial information to modulate the photoelectric material at varying temperature conditions. Declaration of interest None Acknowledgments This work was supported by the National Natural Science Foundation of China [grant number 41404109] and the Science and Technology Development Project of Jilin Province [grant number 20190303108SF]. The authors gratefully thank Dr. Xiao-Qiang Di for the generous use of Gaussian 09 software in this work. References [1] M.M. Mendes-Pinto, E. Sansiaume, H. Hashimoto, B. Robert, Electronic absorption and ground state structure of carotenoid molecules, J. Phys. Chem. B 117 (2013) 11015–11021, https://doi.org/10.1023/A:1014715114520. [2] C. Uragami, K. Saito, M. Yoshizawa, P. Molnár, H. Hashimoto, Unified analysis of optical absorption spectra of carotenoids based on a stochastic model, Arch. Biochem. Biophys. 650 (2018) 49–58, https://doi.org/10.1016/j.abb.2018.04.021. [3] N.J. Fraser, H. Hashimoto, R.J. Cogdell, Carotenoids and bacterial photosynthesis: the story so far…, Photosynth. Res. 70 (2001) 249–256, https://doi.org/10. 1023/A:1014715114520. [4] T. Polívka, V. Sundström, Ultrafast dynamics of carotenoid excited states-from solution to natural and artificial systems, Chem. Rev. 104 (4) (2004) 2021–2071, https://doi.org/10.1021/cr020674n. [5] T. Polívka, H.A. Frank, Molecular factors controlling photosynthetic light harvesting by carotenoids, Acc. Chem. Res. 43 (8) (2010) 1125–1134, https://doi.org/ 10.1021/ar100030m. [6] M. Macernis, D. Galzerano, J. Sulskus, E. Kish, Y.H. Kim, S. Koo, L. Valkunas, B. Robert, Resonance Raman spectra of carotenoid molecules: influence of methyl substitutions, J. Phys. Chem. A 119 (1) (2014) 56–66, https://doi.org/10.1021/jp510426m. [7] M. Macernis, J. Sulskus, S. Malickaja, B. Robert, L. Valkunas, Resonance Raman spectra and electronic transitions in carotenoids: a density functional theory study, J. Phys. Chem. A 118 (10) (2014) 1817–1825, https://doi.org/10.1021/jp406449c. [8] D. Gosztola, M.R. Wasielewski, Resonance Raman spectroscopy of a chlorophyll-porphyrin heterodimer: excitation profile in the 400-450-nm region, J. Phys. Chem. 97 (1993) 9599–9602, https://doi.org/10.1021/j100140a012. [9] M. Bruschi, P.A. Limacher, J. Hutter, H.P. Lüthi, A scheme for the evaluation of Electron delocalization and conjugation efficiency in linearly π-Conjugated systems, J. Chem. Theory Comput. 5 (3) (2009) 506–514, https://doi.org/10.1021/ct8004358. [10] Y.F. Wang, Z.Y. Yu, J. Wu, C.B. Liu, Electron delocalization and charge transfer in polypeptide chains, J. Phys. Chem. A 113 (39) (2009) 10521–10526, https:// doi.org/10.1021/jp9020036.
197
Optik - International Journal for Light and Electron Optics 185 (2019) 191–198
G. Qu, et al.
[11] T. Noguchi, H. Hayashi, M. Tasumi, G.H. Atkinson, Solvent effects on the ag C=C Stretching Mode in the 21Ag− Excited State of β-Carotene and Two Derivatives: Picosecond Time-Resolved Resonance Raman Spectroscopy, J. Phys. Chem. 95 (8) (1991) 3167–3172, https://doi.org/10.1002/chin.199131048. [12] W.L. Liu, Z.R. Zheng, R.B. Zhu, Z.G. Liu, D.P. Xu, H.M. Yu, W.Z. Wu, A.H. Li, Y.Q. Yang, W.H. Su, Effect of pressure and solvent on Raman spectra of all-trans-βcarotene, J. Phys. Chem. A 111 (40) (2007) 10044–10049, https://doi.org/10.1021/jp074048b. [13] N. Gong, H.Y. Fu, S.H. Wang, X.W. Cao, Z.W. Li, C.L. Sun, Z.W. Men, All-trans-β-carotene absorption shift and electron-phonon coupling modulated by solvent polarizability, J. Mol. Liq. 251 (2018) 417–422, https://doi.org/10.1016/j.molliq.2017.12.096. [14] E.J.G. Peterman, T. Pullerits, R. van Grondelle, H. van Amerongen, Electron−phonon coupling and vibronic fine structure of light-harvesting complex II of green plants: temperature dependent absorption and high-resolution fluorescence spectroscopy, J. Phys. Chem. B 101 (22) (1997) 4448–4457, https://doi.org/10. 1021/jp962338e. [15] H. Torii, M. Tasumi, Vibrational structure and temperature dependence of the electronic absorption (11Bu⟵11Ag) of all-trans-β-carotene, J. Phys. Chem. 94 (1) (1990) 227–231, https://doi.org/10.1021/j100364a037. [16] J.A. Burt, X.H. Zhao, J.L. McHale, Inertial solvent dynamics and the analysis of spectral line shapes: Temperature-dependent absorption spectrum of β-carotene in nonpolar solvent, J. Chem. Phys. 120 (9) (2004) 4344–4354, https://doi.org/10.1063/1.1644534. [17] T.Y. Liu, S.N. Xu, Z.W. Li, M.Z. Wang, C.L. Sun, Temperature induced changes in resonance Raman spectra intensity of all-trans-β-carotene: changes in the fundamental, combination and overtone modes, Spectrochim. Acta A Mol. Biomol. Spectrosc. 131 (15) (2014) 153–157, https://doi.org/10.1016/j.saa.2014.04. 069. [18] S. Li, Z.L. Li, S.H. Wang, S.Q. Gao, C.L. Sun, Z.W. Li, The electron–phonon coupling of fundamental, overtone, and combination modes and its effects on the resonance Raman spectra, Mater. Res. Bull. 72 (2015) 1–6, https://doi.org/10.1016/j.materresbull.2015.07.006. [19] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery Jr., J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Ö. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford CT, 2009. [20] C. Castiglioni, M. Tommasini, G. Zerbi, Raman spectroscopy of polyconjugated molecules and materials confinement effect in one and two dimensions, Phil. Trans. R. Soc. Lond. A 362 (2004) 2425–2459, https://doi.org/10.1098/rsta.2004.1448. [21] M.O. Senge, H. Hope, K.M. Smith, Structure and Conformation of Photosynthetic Pigments and Related Compounds 3. Crystal Structure ofβ-Carotene, Z. Naturforsch. C 47 (5-6) (1992) 474–476, https://doi.org/10.1515/znc-1992-0623. [22] S. Schlücker, A. Szeghalmi, M. Schmitt, J. Popp, W. Kiefer, Density functional and vibrational spectroscopic analysis of β‐carotene, J. Raman Spectrosc. 34 (2003) 413–419, https://doi.org/10.1002/jrs.1013. [23] W.L. Liu, Z.G. Wang, Z.R. Zheng, A.H. Li, W.H. Su, Effect of β-ring rotation on the structures and vibrational spectra of β carotene density functional theory analysis, J. Phys. Chem. A 112 (42) (2008) 10580–10585, https://doi.org/10.1021/jp802024v. [24] R.J. Cogdell, H.A. Frank, How carotenoids function in photosynthetic bacteria, B.B.A. Biomembranes 895 (1987) 63–79, https://doi.org/10.1016/S03044173(87)80008-3. [25] H.A. Frank, A.J. Young, G. Britton, R.J. Cogdell, The photochemistry of carotenoids, in: J.Amesz Govindjee, E.M. Aro, J. Barber, R.E. Blankenship, N. Murata, D.R. Ort (Eds.), Carorenoids in Photosynthesis, Kluwer Academic publishers, London, 1992, pp. 137–157. [26] H.A. Frank, R. Frahoosh, M.L. Aldema, B. Decoster, R.L. Christensen, R. Gebhard, J. Lugtenburg, Carotenoid-to-bacteriochlorophyll singlet energy transfer in carotenoid-incorporated B850 light-harvesting complexes of rhodobacter sphaeroides R-26.1, Photochem. Photobiol. 57 (1) (1993) 49–55, https://doi.org/10. 1111/j.1751-1097.1993.tb02254.x. [27] L. Fiedor, J. Heriyanto, M. Fiedor, Pilch, Effects of molecular symmetry on the electronic transitions in carotenoids, J. Phys. Chem. Lett. 7 (10) (2016) 1821–1829, https://doi.org/10.1021/acs.jpclett.6b00637. [28] S.L. Bondarev, S.M. Bachilo, S.S. Dvornikov, S.A. Tikhomirov, S2→S0 fluorescence and transient Sn ⟵ S1 absorption of all-trans-β-carotene in solid and liquid solutions, J. Photochem. Photobio. A 46 (3) (1989) 315–322, https://doi.org/10.1016/1010-6030(89)87048-0. [29] R.J. Thrash, H.L.B. Fang, G.E. Leroi, The Raman excitation profile spectrum of β-carotene in the preresonance region: evidence for a low-lying singlet state, J. Chem. Phys. 67 (12) (1977) 5930–5933, https://doi.org/10.1063/1.434800. [30] A. Dreuw, P.H.P. Harbach, J.M. Mewes, M. Wormit, Quantum chemical excited state calculations on pigment–protein complexes require thorough geometry reoptimization of experimental crystal structures, Theor. Chem. Acc. 125 (2010) 419–426, https://doi.org/10.1007/s00214-009-0680-3. [31] M.M. Mendes-Pinto, E. Sansiaume, H. Hashimoto, A.A. Pascal, A. Gall, B. Robert, Electronic absorption and ground state structure of carotenoid molecules, J. Phys. Chem. B 117 (38) (2013) 11015–11021, https://doi.org/10.1021/jp309908r. [32] W.R. Salaneck, O. Inganäs, B. Thémans, J.O. Nilson, B. Sjögren, J.E. Osterholm, J.L. Brédas, S. Svensson, Thermochromism in poly(3hexylthiophene) in the solid state: a spectroscopic study of temperature dependent conformational defects, J. Chem. Phys. 89 (8) (1988) 4613–4619, https://doi.org/10.1063/1.454802. [33] J.M. Dudik, C.R. Johnson, S.A. Asher, Wavelength dependence of the preresonance Raman cross sections of CH3CN, SO42−, ClO4−, and NO3−, J. Chem. Phys. 82 (4) (1985) 1732–1740, https://doi.org/10.1063/1.448405. [34] N. Biswas, S. Umapathy, Simple approach to determining absolute Raman cross sections using an optical parametric oscillator, Appl.Spectrosc. 52 (4) (1998) 496–499, https://doi.org/10.1366/0003702981944021. [35] D.Yu. Paraschuk, V.M. Kobryanskii, Coherent electron-lattice vibrations in trans-nanopolyacetylene probed by raman scattering, Phys.Rev.L 87 (20) (2001) 207402, https://doi.org/10.1103/PhysRevLett.87.207402 (1-4). [36] G. Orlandi, F. Zerbetto, M.Z. Zgierski, Theoretical analysis of spectra of short polyenes, Chem. Rev. 91 (5) (1991) 867–891, https://doi.org/10.1021/ cr00005a012. [37] B. Kirtman, C.E. Dykstra, B. Champagne, Major intermolecular effects on nonlinear electrical response in a hexatriene model of solid state polyacetylene, Chem. Phys. Lett. 305 (1999) 132–138, https://doi.org/10.1016/S0009-2614(99)00375-9. [38] D.Yu. Paraschuk, V.M. Kobryanskii, Synchronous Electron–Nuclear vibrations in a π-Conjugated nanopoly(acetylene) chain, JETP Lett. 73 (2001) 170–174, https://doi.org/10.1134/1.1364545.
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