Electron velocity map imaging and theoretical study on CuXH (X = O and S) anions

Accepted Manuscript Electron velocity map imaging and theoretical study on CuXH (X=O and S) anions

Zhengbo Qin, Hui Wang, Yangdi Ren, Xianfeng Zheng, Zhifeng Cui, Zichao Tang PII: DOI: Reference:

S1386-1425(17)30516-4 doi: 10.1016/j.saa.2017.06.039 SAA 15255

To appear in:

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

Received date: Revised date: Accepted date:

15 February 2017 27 June 2017 30 June 2017

Please cite this article as: Zhengbo Qin, Hui Wang, Yangdi Ren, Xianfeng Zheng, Zhifeng Cui, Zichao Tang , Electron velocity map imaging and theoretical study on CuXH (X=O and S) anions, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy (2017), doi: 10.1016/j.saa.2017.06.039

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Electron velocity map imaging and theoretical study on CuXH (X=O and S) anions

Zhengbo Qina,, Hui Wanga, Yangdi Rena, Xianfeng Zhenga, and Zhifeng Cuia, and

RI

a

PT

Zichao Tangb,,

Anhui Province Key Laboratory of Optoelectric Materials Science and Technology,

b

NU

SC

Department of Physics, Anhui Normal University, Wuhu, Anhui 241000, China

State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of

MA

Chemistry, College of Chemistry and Chemical Engineering, Xiamen University,

AC

CE

PT E

D

Xiamen 361005, China

*

Corresponding authors: Email: [email protected] (Z.B.Q.), [email protected]

(Z.C.T.)

1

ACCEPTED MANUSCRIPT ABSTRACT Vibrationally resolved photoelectron spectra of CuOH– and CuSH– have been determined via velocity map imaging method to investigate the transitions of X1A'← X2A' at 532 nm. Adiabatic detachment energies of CuOH– and CuSH– are assigned to 0.995(12) and 1.098(12) eV, respectively. Combined theoretical calculations with

PT

Franck-Condon simulations, it allows extracting the vibrational frequencies in neutral,

RI

which yields 629(32) cm-1 with Cu-O stretching mode and 387(24) cm-1 with Cu-S

SC

stretching mode for CuXH (X = O and S). Parallel transition properties of photoelectron angular distributions (PADs) for both species are correlated to the

NU

photodetachment of SOMO orbitals, which mainly involved in the Cu atom s orbital and partial s orbital in other atoms. Based on chemical bonding analyses (Wiberg,

MA

NAO, Mayer, NRT, and ELF), it is suggested that a trend is observed with a subtle variation of covalent component from weak covalent behavior between Cu-O in

D

CuOH–1/0 to stronger covalent bonding between Cu-S in CuSH–1/0 (especially for

PT E

non-ignorable covalent component in CuSH species) though ionic bonding dominates

AC

CE

both in Cu-O and Cu-S bonds for the two systems.

2

ACCEPTED MANUSCRIPT I. INTRODUCTION There are many studies on the noble metal catalysis on water to produce hydrogen and hydroxyl groups [1]. One process possibly includes dissociated OH fragment binding or migrating on surface. In copper surface catalysis process, H2O (or H2S) adsorption on the surface may become to dissociative chemical adsorption [2-5].

PT

OH or SH fragments may be bonding or migrating on a specific active site. Studying

RI

the chemical binding capabilities between copper and those functional groups is

SC

significant for understanding surface chemical reaction for copper atom interacting with H2O and H2S etc. solvent molecules. In the gas phase, the bond properties

NU

between the basic unit Cu atom and these functional groups are less well known. The interaction of the thiols with noble metal surfaces and interfaces (especially

MA

for gold) is of considerable interest for the design of new functional materials in molecular electronics, surface modification and heterogeneous catalysis [6, 7].

D

Recently, quite large covalence is revealed for the Au-S bond in varies

PT E

thiolate-protected gold nanoparticles and self-assembled monolayers [8]. However, little concerns are given to the copper-sulfur interactions study. One possible reason is

CE

that copper is more activated than gold in ambient conditions. From another point of view, activated copper has more application in real life and catalytic reactions, which

AC

should be concerned more in detailed copper-sulfur complexes in the gas phase. The interactions of noble metal atom with H2O have been extensively studied [9-20]. Both theoretical and experimental evidences suggest that M–(H2O) (M = Cu, Ag, Au) belong to a planar structure with the hydrogen atoms oriented toward the metal anion, whereas the neutral counterparts have the structure features of the oxygen atom oriented toward the metal atoms [10-15, 18]. Some spectroscopic and computational work has also been reported for CuOH–1/0 [11, 21-23]. Both neutral and 3

ACCEPTED MANUSCRIPT anion were characterized as obtuse bond angles [11, 21, 22]. Previous reported results about AuOH and AgOH have suggested that there are quite large geometric changes upon photodetachment with a displacement of ～0.15 Å in the AuOH– → AuOH and AgOH– → AgOH transitions [17, 20, 24]. The vibrational frequencies obtained in the experiment are mainly involved in M-O stretching mode (M = Au and Ag). For the

PT

completely understanding the geometric evolution trend upon photodetachment for

RI

the noble metal-OH complexes family, and for the comparison of bond nature

SC

difference between Cu and XH functional group (X = O and S), we have conducted anion photoelectron imaging experiment and theoretical investigation on CuXH (X=O

NU

and S) anions and neutral counterparts.

II. EXPERIMENTAL AND THEORETICAL METHODS

MA

The photoelectron velocity-map imaging system has been described in detail elsewhere and we only give a brief description here [25]. A small amount of CuOH–

D

and CuSH– anions under current study are likely the products of secondary reactions

PT E

through collision induced dissociation (CID) process in the reaction of copper anion with trace methanethiol or water in the presence of a supersonic beam of helium

CE

(99.999%) carrier gas. The anions were introduced to a McLaren-Wiley time-of-flight, mass selected, and crossed with a laser beam (Nd:YAG laser). The resulting

AC

photoelectrons were extracted by a velocity map imaging photoelectron spectrometer and recorded by a charge-coupled device camera. Each image was accumulated with 10 000–50 000 laser shots at 10 Hz repetition rate. The final raw image stood for the projection of the photoelectron density in the 3D laboratory frame onto the 2D imaging detector. The original 3D distribution was reconstructed using the Basis Set Expansion (BASEX) inverse Abel transform method [26], and the photoelectron spectrum was acquired. The photoelectron kinetic energy spectra were calibrated by 4

ACCEPTED MANUSCRIPT the known spectra of Cu– and S–. The photoelectron spectra (PES) were plotted against electron binding energy eBE = hν - eKE, where hν is the photon energy. The typical energy resolution was about 25 meV full width at half maximum (FWHM) at electron kinetic energy (eKE) of 1 eV (～2.5%). The photoelectron angular distribution (PAD) is obtained by integrating the

PT

intensity of the Abel-inverted image. The PADs in the one-photon process with

(1)

SC

I(θ) = k[1+ βP2(θ)]

RI

linearly polarized light are generally described by the function: [27, 28]

where θ is the angle between the electron velocity vector and the laser

NU

polarization direction in the laboratory frame, k is a normalization constant proportional to the total photodetachment cross-section, and P2 is the second-order

MA

Legendre polynomials. The angular dependence is completely defined by β, the anisotropy parameter, which can be determined by fitting eq. (1) to the experimental

D

PAD.

The

augmented

PT E

All theoretical calculations were carried out using the Gaussian09 package [29]. correlation-consistent

polarized

valence

triple-ζ

basis

set

CE

aug-cc-pVTZ-pp [30-32] with the relativistic effective small core pseudopotentials was used for the copper, silver, and gold atom, and aug-cc-pVTZ [33] for other atoms.

AC

The double-hybrid density functional theory (mPW2PLYP) and CCSD(T) methods are used to predict the geometric structures of anionic and neutral complexes [34], which has been successfully examined for benchmark study in similar systems [35]. Vibrational analysis was employed at the harmonic level to check it out whether the optimized structures were the true local minima or not. All the energies of the optimized structures were reevaluated at the level of coupled cluster CCSD(T) including zero-point vibrational energy (ZPVE) corrections [36]. The adiabatic 5

ACCEPTED MANUSCRIPT detachment energy (ADE) was defined as the energy of the origin transition between the ground state of the anion and the neutral, which also represents the electron affinity of neutral species. The vertical detachment energy (VDE) was defined as the energy difference between the ground state of the anion and the neutral at the anionic geometry. Natural resonance theory (NRT) [37-39] based on natural bond orbitals

PT

(NBO) method [40] and electron localization function (ELF) analyses [41] were

RI

performed to further understand the nature of the chemical bonding in CuXH–1/0 (X = O and S). For comparison in the ELF analyses, mPW2PLYP method is used to predict

SC

the geometric structures for MXH–1/0 (M=Cu, Ag, and Au; X = O and S) complexes.

NU

III. RESULTS AND DISCUSSIONS _

MA

a)CuOH

0.4

0.8

1.2

1.6

2.0

1.2

1.6

2.0

b)CuSH

0.4

0.8

Electron Binding Energy (eV)

CE

PT E

D

_

Fig. 1. Photoelectron images (left columns) and spectra (right columns) for (a) CuOH–

AC

and (b) CuSH– obtained at 532 nm. The left side shows the raw photoelectron image (left) and the reconstructed one (right) after inverse Abel transformation. Each photoelectron velocity-image consists of raw image (left part) and the reconstructed image (right part) after inverse Abel transformation. The double arrow shows the direction of the laser polarization.

6

ACCEPTED MANUSCRIPT The photoelectron velocity map imaging of CuOH– and CuSH– are displayed in Fig. 1 and exhibit clear-cut vibrational structure. Based on the averaged peak-spacing, the vibrational frequencies are measured to be 629(32) cm-1 and 387(24) cm-1 for CuOH and CuSH, respectively. From 0-0 vibrational transitions, we deduced the ADE of each anion, to be 0.995(12) and 1.098(12) eV for CuOH– and CuSH–, respectively.

PT

The corresponding VDEs, determined from each band maximum, are 0.995(12) and

RI

1.145(12) eV for CuOH– and CuSH–, respectively (Table 1). The single sequence of

SC

vibrational peaks possibly implies that only one vibrational mode is activated for each species upon photodetachment as will be evidenced in the following Franck-Condon

Anion

Neutral

(0.419)

1A'

(0.445)

MA

2A'

NU

simulations and borne out from ab initio calculations.

1. 758 (0.778)1. 766 (-1.224)

1. 846 (-0.151)1. 788 (-1.268)

D

(0.099)

1A'

PT E

2A'

(0.123)

2.092 (0.601) 2.120 (-0.724)

CE

2.188 (-0.232) 2.216 (-0.867)

Fig. 2. Optimized structures of CuOH– and CuSH– as well as their neutral

AC

counterparts. Selected bond lengths (in Å) calculated at the level of mPW2PLYP/aug-cc-pVTZ(-pp) are indicated in black, while the bond lengths calculated

at the level of CCSD(T)/aug-cc-pVTZ(-pp) for CuOH–1/0 and CCSD(T)/aug-cc-pVDZ(-pp) –1/0

for CuSH

are indicated in italic and red. The NPA charges are labeled in

parentheses on Cu, O or S, and H atoms (blue) (See text for details).

7

ACCEPTED MANUSCRIPT _

a)CuOH

Exp. FC fit Stick

ν3

* 1.0

1.2

1.4

ν3

_

* 1.0

1.2

SC

RI

b)CuSH

0.8

1.6

PT

0.8

1.4

1.6

NU

Electron Binding Energy (eV)

Fig. 3. Franck–Condon (FC) simulation for the photodetachment of (a) CuOH─ and (b) 0.98 SCALE CuOH:260K 0.032ev

MA

0.030ev CuSH─. Black curve stands for CuSH:175K the experimental data, blue curves for Franck–Condon

(FC) simulated results, and red sticks for simulated vibronic transitions. An asterisk in

PT E

D

each spectrum designates hot band transitions.

Theoretical calculations were carried out to elucidate the geometric and

CE

electronic properties of CuOH–1/0 and CuSH–1/0 species. All of them possess Cs symmetry and detailed geometric parameters are demonstrated in Fig. 2. When

AC

different methods (mPW2PLYP and CCSD(T)) are used, the Cu-X bond length is the predominant structure variation over the X-H bond length and ∠Cu-X-H (X = O and S), especially for anions. Compared the Cu-X bond calculated at the level of mPW2PLYP, CCSD(T) results show the significant decrease of the Cu-O bond length by 0.058 Å in CuOH–1 and increment of the Cu-S bond length by 0.028 Å in CuSH–1/0, respectively. The natural charge population analyses (NPA) are labeled in parentheses in Fig. 2. It indicates that the vast majority of charge (~93% for CuOH– and ~83% for 8

ACCEPTED MANUSCRIPT CuSH–) is removed from the Cu atom (-0.15 → 0.78 e in CuOH– → CuOH and -0.23 → 0.60 e in CuSH– → CuSH). This scenario is in accordance with molecular orbital analysis which reveals that the excess electron in CuOH– and CuSH– is detached from a singly occupied molecular orbital (SOMO). As shown in Fig. 4, this SOMO has a significant s-orbital (60% Cu(s) + 2% O(s) + 2% H(s) in CuOH– and 54%

PT

Cu(s) + 15% S(s) + 5% H(s) in CuSH–). Also the original orbital nature of detached

RI

electrons is borne out in anisotropy parameter, β. More concretely, the electron ejected

SC

from s orbital forms P wave, which corresponds to a positive β value [42] (herein, β ~

NU

1.7 for CuOH– and β ~ 1.0 for CuSH–).

PT E

D

CuOH–

MA

SOMO

CE

CuSH–

AC

Fig. 4. The contour plots of the highest occupied molecular orbitals of the ground state of CuOH– and CuSH– calculated at the level of mPW2PLYP/aug-cc-pVTZ(-pp) (iso = 0.04 a.u.). (Blue and red colors stand for different phases of molecular orbital).

9

ACCEPTED MANUSCRIPT Table 1. Observed and Calculated adiabatic detachment energies (ADEs) and vertical detachment energies (VDEs) for the ground state of anionic and neutral CuXH─ (X=O and S) including ZPVEs (Unit: eV). Cal.

Expt.a State

A'

CuOH

1

A'

CuSH─

2

A'

CuSH

1

A'

VDE

ADE

VDE

0.995(12)

0.995(12)

0.960

1.011

1.098(12)

1.145(12)

1.071

ADE

1.117

VDE

0.504c

0.513c

1.070d

1.142d

Numbers in the parentheses are experimental uncertainties in the last digit.

b

mPW2PLYP

represents

the

NU

a

ADE

PT

2

CCSD(T)

RI

CuOH─

mPW2PLYPb

SC

Species

method

calculated

at

the

level

of

c

MA

CCSD(T)/aug-cc-pVTZ(-pp)//mPW2PLYP/aug-cc-pVTZ(-pp).

Both single point energy calculation and geometries optimization calculated at the level of

CCSD(T)/aug-cc-pVTZ(-pp). d

AC

CE

PT E

D

CCSD(T)/aug-cc-pVTZ(-pp)//CCSD(T)/aug-cc-pVDZ(-pp)

10

ACCEPTED MANUSCRIPT Table 2. Calculated vibrational frequencies (scaled by 0.98) of CuXH (X=O and S) anions using the aug-cc-pVTZ-(pp) basis sets compared to experimental observations (cm-1). ν1, ν2, and ν3 represent X-H stretching, Cu-X-H bending, and Cu-X stretching modes, respectively. Numbers in the parentheses are experimental uncertainties in the last digit.

ν2

3733 643

Exp.

600

ν1

ν2

3757 780

580(32)

mPW2PLYP

2621

475

306

NU

CuSH

ν3

RI

CuOH mPW2PLYP

ν1

SC

Species/Method

Neutral

PT

Anion

305(32)

631 629(32) 395 387(24)

MA

Exp.

2639 607

ν3

To aid in the spectral assignment, we conducted Franck-Condon simulations on

D

both cases with the PESCAL program which is based on harmonic oscillator

PT E

approximation including Duschinsky rotation via the Rosenstock-Chen method to calculate Franck-Condon factors [43] and present the results in Fig. 3. The individual

CE

vibrational band contours are generated using Gaussian line shapes with a full width at half maxima (FWHM) of 32 meV for CuOH─ and 30 meV for for CuSH─.

AC

Simulations were run including all normal modes and the simulated vibrational temperature of the anion was obtained at ∼260 K for CuOH─ and ∼180 K for CuSH─ to yield a best match between the simulated and experimental spectra. Theoretical harmonic frequencies of neutrals were scaled to match the experimental frequencies, with scaling factors of 0.98, and the origin of the simulated spectrum was shifted to the experimental band origin. For qualitatively evaluating vibrational frequencies, we adjust the normal mode displacement vectors to fit the experimental spectra on the 11

ACCEPTED MANUSCRIPT basis of theoretical Franck-Condon simulations. As revealed by simulation, Cu-X (X=O and S) stretching mode ν3 has the dominant effect on the spectra and vibrational frequencies of anion are extracted (580(32) cm-1 with Cu-O stretching mode in CuOH─ and 305(32) cm-1 with Cu-S stretching mode in CuSH─). In term of simulation, the adiabatic electron affinities are obtained to be 0.995(12) eV for

PT

CuOH─ and 1.098(12) eV for CuSH─, which are in excellent agreement with the

RI

theoretical values of 0.960 eV for CuOH─ and 1.071 eV for CuSH─ calculated at the level of CCSD(T)/aug-cc-pVTZ(-pp)//mPW2PLYP/aug-cc-pVTZ(-pp), respectively (Table 1).

SC

However, one exception is CuOH─, of which the ADE and VDE using CCSD(T)

NU

method are in poor agreement with the experimental ones, respectively. The vibrational frequencies in the photoelectron spectra of neutral counterparts are

MA

dominated by the Cu-O or Cu-S stretching mode (ν3), which are determined to be 629(32) cm-1 for CuOH and 387(24) cm-1 for CuSH. This situation is consistent with

D

relatively large bond length displacement as shown in Fig. 2 (0.088 Å for the Cu-O

PT E

bond and 0.096 Å for the Cu-S bond upon detachment of the excess electron). All the

CE

theoretical vibrational frequencies and experimental ones are displayed in Table 2.

Table 3. Calculated singly occupied molecular orbital (SOMO) compositions at the

AC

level of mPW2PLYP/aug-cc-pVTZ(-pp) level of CuOH– and CuSH–.

MO

MO energy level (eV)

MO pop. analysis: % M character Cu

X=O or S

H

2(s)+5(p)

5(s)

CuOH– SOMO

0.11

60(s)+27(p)+1(d) CuSH–

SOMO

-0.01

54(s)+12(p)+1(d) 15(s)+12(p) 12

5(s)

ACCEPTED MANUSCRIPT

Chemical bonding nature in the CuOH– and CuSH– complexes can be qualitatively inferred from molecular orbital (MO) contours as depicted in Fig. 4. Strong covalent character of Cu-S bond in CuSH–1 in contrast to Cu-O bond in CuOH–1 are borne out in SOMO profile (Fig. 4 and Table 3), where Cu s and p

PT

orbitals (66% s and p orbitals) more greatly overlap with S s and p orbitals (27% s and

RI

p orbitals) to form antibonding σ* in contrast to the formation of antibonding σ*

NU

SC

bonding in CuOH–1 (87% Cu s and p orbitals and 7% O s and p orbitals).

NAO

Mayer

0.370

0.621

0.455

1.006

0.574

0.642

0.718

1.202

Table 4. Theoretical Cu-X (X = O and S) bond orders at the level of mPW2PLYP. Wiberg

anion

0.248

neutral

0.427

anion

0.404

MA

Bond order

0.706

CE

neutral

PT E

Cu-SH

D

Cu-OH

To gain more insights into the chemical bonding difference between the CuOH–

AC

and CuSH–, we employed bond orders calculation based on various theoretical schemes. As listed in Table 4, three methods give a larger Cu–S bond order in CuSH– relative to CuOH–. These results also give strong evidence that Cu-S or Cu-O bond orders in neutrals is nearly 2 times of that in anions (Wiberg and Mayer bond orders), which is in accordance with the classic chemical bond order trend that excess an electron in σ* bonding reduces the bond order. Natural resonance theory (NRT) is a theoretical method based on quantum chemical calculations to describe molecules 13

ACCEPTED MANUSCRIPT with significant resonance structures in terms of classic valence-bond concepts. It provides detailed covalent and ionic electrovalent contributions for CuOH–1/0 or CuSH–1/0 complexes. As shown in Table 5, it is found that the covalent contributions to the Cu–O bond in CuOH– and Cu-S bond in CuSH– are 0.20 and 0.26, respectively, while it increases to 0.35 for Cu-S bond in CuSH. Thus, excess electron largely

PT

influences the covalent contributions in CuSH– in contrast to CuOH– where nearly no

RI

change occurs. The chemical bonding can be further glimpsed from the electron

SC

localization functions (ELFs), which is a visual tool to estimate the probability of finding electron pairs in space, and an ELF analysis can show the difference among

NU

covalent bonds, ionic bonds, and lone pairs [44, 45]. As displayed in Fig. 5a-d, a subtle increase of electron pairing density between the Cu and S atoms exists in

MA

CuSH– compared to CuOH–, whereas more stronger electron pairing density is found in Fig. 5d for CuSH. The covalent interaction between Cu and X ligand (X = O and S)

D

is more clearly illustrated in the one-dimensional projections of electron localization

PT E

functions along the Cu-X bond axis (X = O and S) presented in Fig. 5e and Fig. 5f (i.e. electron pairing density: 0.110 and 0.135 a.u. for CuOH─ and CuOH, respectively;

CE

electron pairing density: 0.143 and 0.173 a.u. for CuSH─ and CuSH, respectively). The observations are in consistent with the evolutions analyzed from MO contours

AC

and chemical bond orders. It is interesting to fully understanding the covalent feature of CuXH-1/0 (X = O and S) and its Ag and Au analogs. As displayed in Fig. 6 (also compared with that in Fig. 5), it reveals that M-S (M = Cu, Ag, Au) bond has more covalent characters than the M-O (M = Cu, Ag, Au) bond both in anions and neutrals, and considerable electron pairing density exists between M-S (M = Cu, Ag, Au) bonds with the strongest covalent character in AuSH. 14

ACCEPTED MANUSCRIPT Table 5. Summary of natural resonance theory (NRT) and covalent and ionic electrovalent contributions of the optimized structures of [CuXH]─ (X = O and S)

NRT bond order

% covalent

% ionic

[Cu-OH]−

0.5011

0.1006c + 0.4006i

20.08

79.92

[Cu-OH]

1.0000

0.1958c + 0.8042i

19.58

80.42

[Cu-SH]−

0.5017

0.1315c + 0.3702i

26.21

73.79

[Cu-SH]

1.0031

0.3478c + 0.6554i

34.67

65.33

SC

RI

T(NRT)a

Total NRT bond order is the sum of covalent (c) plus ionic (i) bond order.

NU

a

Species

PT

species.

a) CuOH–

c) CuSH–

H

O

b) CuOH

Cu

MA

H Cu

S

d) CuSH H

D

H

Cu

PT E (a.u.) Value(a.u.) Value

CE

1.0 1.0 e) CuOH-1/0 0.8 0.8

S

anion neutral

0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0

1.0 1.0 (a.u.) Value(a.u.) Value

AC

Cu

O

0.8 0.8

0.135 0.1100.135 0.110

Position O Cu Position (Bohr) (Bohr) f)

CuSH-1/0

anion neutral

0.6 0.6 0.4 0.4 0.2 0.2 0.0 0.0

Cu

0.143 0.143

0.173 0.173

S

Position Position (Bohr) (Bohr)

Fig. 5. The electron localization functions (ELF) for (a) CuOH−, (b) CuOH, (c) CuSH−, and (d) CuSH. And one-dimensional projections between Cu-O or Cu-S bond for CuOH–1/0 or CuSH–1/0 are illustrated in (e) and (f) figures, respectively (Unit: a.u.). 15

ACCEPTED MANUSCRIPT

a) AgOH–

H

H O

Ag

H

H O

Au

c) AgOH

SC

g) AgSH

H

H O

Ag

S

h) AuSH

MA

d) AuOH H O

H

Au

S

PT E

D

Au

S

NU

Ag

PT

f) AuSH–

b) AuOH–

Au

S

RI

Ag

e) AgSH–

Fig. 6. The electron localization functions (ELF) for (a) AgOH−, (b) AuOH−, (c)

AC

CE

AgOH, (d) AuOH, (e) AgSH−, (f) AuSH−, (g) AgSH, and (h) AuSH (Unit: a.u.).

IV. CONCLUSIONS We have investigated spectral and chemical bonding properties of basic unit of CuOH−1/0 and CuSH−1/0 via a joint of high-resolution velocity-map imaging photoelectron spectroscopy and theoretical model. The ADEs of these anionic complexes have been measured to be 0.995(12) eV and 1.098(12) eV for CuOH─ and CuSH─, respectively. In addition, analysis of experimental spectra yields the ν3 of 629(32) and 387(24) for CuOH and CuSH, respectively. Extensively chemical 16

ACCEPTED MANUSCRIPT bonding analyses indicate that subtle evolution of covalent properties are affected by the coordinate atoms (O or S atom in this work) with copper and charge state. More covalent bond nature is found in Cu-S bond and neutral state (CuSH).

ACKNOWLEDGMENTS

PT

This work is supported by the National Science Foundation of China (Grant No.

RI

21273233 11674003, 61475001, and 21503003), the Ministry of Science and

SC

Technology of China (Grant No. 2011YQ09000505), Anhui Natural Science Foundation (Grant No. 1608085QA10), Anhui University Natural Science Foundation

NU

(Grant No. KJ2015A032), and Startup Foundation for doctors in Anhui Normal University. We also acknowledge additional support from Special Program for

MA

Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the

AC

CE

PT E

D

second phase) and Super Computation center of Shenzhen.

17

ACCEPTED MANUSCRIPT References [1] G.B. Fisher, B.A. Sexton, Phys. Rev. Lett., 44 (1980) 683-686. [2] P.A. Thiel, T.E. Madey, Surf. Sci. Rep., 7 (1987) 211-385. [3] M.A. Henderson, Surf. Sci. Rep., 46 (2002) 1-308. [4] K.T. Leung, X.S. Zhang, D.A. Shirley, J. Phys. Chem., 93 (1989) 6164-6170.

PT

[5] A. Galtayries, J.P. Bonnelle, Surf. Interface Anal., 23 (1995) 171-179.

RI

[6] M.-C. Daniel, D. Astruc, Chem. Rev., 104 (2004) 293-346.

SC

[7] J.C. Love, L.A. Estroff, J.K. Kriebel, R.G. Nuzzo, G.M. Whitesides, Chem. Rev., 105 (2005) 1103-1169.

NU

[8] C.G. Ning, X.G. Xiong, Y.L. Wang, J. Li, L.S. Wang, Phys. Chem. Chem. Phys., 14 (2012) 9323-9329.

MA

[9] P. Neogrády, M. Urban, A.J. Sadlej, J. Mol. Struct. (Theochem), 332 (1995) 197-207.

D

[10] I. Pápai, J. Chem. Phys., 103 (1995) 1860-1870.

PT E

[11] C.G. Zhan, S. Iwata, Chem. Phys. Lett., 232 (1995) 72-78. [12] C. Adamo, F. Lelj, J. Mol. Struct. (Theochem), 389 (1997) 83-89.

CE

[13] A. Antušek, M. Urban, A.J. Sadlej, J. Chem. Phys., 119 (2003) 7247-7262. [14] F. Muntean, M.S. Taylor, A.B. McCoy, W.C. Lineberger, J. Chem. Phys., 121

AC

(2004) 5676-5687.

[15] M.S. Taylor, F. Muntean, W.C. Lineberger, A.B. McCoy, J. Chem. Phys., 121 (2004) 5688-5699. [16] G.J. Rathbone, T. Sanford, D. Andrews, W.C. Lineberger, Chem. Phys. Lett., 401 (2005) 570-574. [17] W. Zheng, X. Li, S. Eustis, A. Grubisic, O. Thomas, H. de Clercq, K. Bowen, Chem. Phys. Lett., 444 (2007) 232-236. 18

ACCEPTED MANUSCRIPT [18] D.-Y. Wu, S. Duan, X.-M. Liu, Y.-C. Xu, Y.-X. Jiang, B. Ren, X. Xu, S.H. Lin, Z.-Q. Tian, J. Phys. Chem. A, 112 (2008) 1313-1321. [19] Y. Gao, W. Huang, J. Woodford, L.-S. Wang, X.C. Zeng, J. Am. Chem. Soc., 131 (2009) 9484-9485. [20] C.X. Chi, H. Xie, Y.Z. Li, R. Cong, M.F. Zhou, Z.C. Tang, J. Phys. Chem. A, 115

PT

(2011) 5380-5386.

RI

[21] S. Ikeda, T. Nakajima, K. Hirao, Mol. Phys., 101 (2003) 105-110.

SC

[22] S. Wang, A. Paul, N.J. DeYonker, Y. Yamaguchi, H.F. Schaefer, J. Chem. Phys., 123 (2005) 014313.

NU

[23] C. Tao, C. Mukarakate, S.A. Reid, Chem. Phys. Lett., 449 (2007) 282-285. [24] B.R. Visser, M.A. Addicoat, J.R. Gascooke, X. Zhang, K. Bowen, W.D.

MA

Lawrance, G.F. Metha, Chem. Phys. Lett., 625 (2015) 164-167. [25] Z. Qin, X. Wu, Z. Tang, Rev. Sci. Instrum., 84 (2013) 066108.

PT E

(2002) 2634-2642.

D

[26] V. Dribinski, A. Ossadtchi, V.A. Mandelshtam, H. Reisler, Rev. Sci. Instrum., 73

[27] C.N. Yang, Phys. Rev., 74 (1948) 764-772.

CE

[28] Y. Ogi, H. Kohguchi, D. Niu, K. Ohshimo, T. Suzuki, J. Phys. Chem. A, 113 (2009) 14536-14544.

(2009).

AC

[29] M.J. Frisch, G.W. Trucks, H.B. Schlegel and e. al., Gaussian 09, revision D.01.

[30] R.A. Kendall, J.T.H. Dunning, R.J. Harrison, J. Chem. Phys., 96 (1992) 6796-6806. [31] D.E. Woon, J.T.H. Dunning, J. Chem. Phys., 98 (1993) 1358-1371. [32] K.A. Peterson, C. Puzzarini, Theor. Chem. Acc., 114 (2005) 283-296. [33] J.T.H. Dunning, J. Chem. Phys., 90 (1989) 1007-1023. 19

ACCEPTED MANUSCRIPT [34] T. Schwabe, S. Grimme, Phys. Chem. Chem. Phys., 8 (2006) 4398. [35] Z. Qin, Z. Liu, R. Cong, H. Xie, Z. Tang, H. Fan, J. Chem. Phys., 140 (2014) 114307. [36] G.E. Scuseria, C.L. Janssen, H.F. Schaefer Iii, J. Chem. Phys., 89 (1988) 7382-7387.

PT

[37] E.D. Glendening, F. Weinhold, J. Comput. Chem., 19 (1998) 593-609.

RI

[38] E.D. Glendening, F. Weinhold, J. Comput. Chem., 19 (1998) 610-627.

SC

[39] E.D. Glendening, J.K. Badenhoop, F. Weinhold, J. Comput. Chem., 19 (1998) 628-646.

NU

[40] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev., 88 (1988) 899-926. [41] T. Lu, F. Chen, J. Comput. Chem., 33 (2012) 580-592.

MA

[42] J. Cooper, R.N. Zare, J. Chem. Phys., 48 (1968) 942-943. [43] K.M. Ervin, T.M. Ramond, G.E. Davico, R.L. Schwartz, S.M. Casey, W.C.

D

Lineberger, J. Phys. Chem. A, 105 (2001) 10822-10831

PT E

[44] A.D. Becke, K.E. Edgecombe, J. Chem. Phys., 92 (1990) 5397-5403. [45] A. Savin, O. Jepsen, J. Flad, O.K. Andersen, H. Preuss, H.G. von Schnering,

AC

CE

Angew. Chem., Int. Ed., 31 (1992) 187-188.

20

ACCEPTED MANUSCRIPT _

a)CuOH

Exp. FC fit Stick

ν3

*Graphical abstract 0.8 a)CuOH

0.8

1.0

1.2

1.4

1.6 0.8

1.0

1.2

1.4

Electron Binding Energy (eV) 0.98 SCALE CuOH:260K 0.032ev CuSH:175K 0.030ev

1.0

1.2

1.4

1.6

Electron Binding Energy (eV)

AC

CE

PT E

D

MA

NU

0.98 SCALE CuOH:260K 0.032ev CuSH:175K 0.030ev

SC

0.8

21

1.6

ν3

RI

b)CuSH

1.4

b)CuSH

ν3

_

1.2

_

Exp. FC fit Stick

ν3

1.0

1.6

PT

_

ACCEPTED MANUSCRIPT *Highlights 

Electron affinities and vibrational frequencies of neutral CuOH and CuSH were accurately measured and assigned by combining the electron velocity map imaging spectroscopy and theoretical calculations.



Parallel transition properties of photoelectron angular distributions (PADs) for

PT

both species are correlated to the Cu atom s orbital and partial s orbital in other

SC

Chemical bonding analyses indicate that a trend of weak covalent behavior is

CE

PT E

D

MA

NU

investigated in CuOH–1/0 and CuSH–1/0 systems.

AC



RI

atoms.

22