Suportting Information For
Vanadium Cluster Neutrals Reacting with Water: Superatomic
Features and Hydrogen Evolution in a Fishing Mode
Hanyu Zhang,†,# Mingzheng Zhang,‡,# Yuhan Jia,† Lijun Geng,† Baoqi Yin,† Shunning Li,‡
Zhixun Luo*† and Feng Pan*‡
† Beijing National Laboratory of Molecular sciences (BNLMS), State Key Laboratory for Structural
Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China; University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
‡ School of Advanced Materials, Peking University Shenzhen Graduate School, Shenzhen 518055, P. R.
China.
# Theses authors contributed equally to this work.
Contents
S1. Methods ...2
1.1 Experimental Methods...2
1.2 Theoretical Methods...2
S2. Supplementary Experiments...5
S3. Structures and Energetics of Vn...9
S4. Partial Charges and Frontier Orbitals ...15
S5. VnH2O Clusters...18
S6. Hydrogen Evolution Reaction ...23
S1. Methods
1.1 Experimental Methods
The deep ultraviolet (DUV) laser ionization time-of-flight mass spectrometer (TOFMS)1
equipped with a fast-flow reaction tube was utilized to conduct the gas-phase experiments of the neutral vanadium clusters Vn (n=1-40) reacting with deuterated water (D2O). A brief
description of the apparatus is given here while detailed information can be found in our previously published studies.2-7 The vanadium clusters (V
n) were generated in the cluster
formation channel after laser ablation of a vanadium disk (99.9% purity), with He (99.999%, 1.0 MPa backing pressure) as the buffer gas. After ablation and cluster generation, the molecular beam flowed to the reaction tube where 2% D2O/He vapor was injected by a pulsed
general valve (Parker, Serial 9). At the end of the reaction tube, the electric field (DC 200 V) is designed to remove unwanted ions from the molecular beam. The molecular beam was allowed for free expansion and sampling via a 2.0 mm skimmer, which separated the differentially pumped chambers. Then the beam of neutral clusters was ionized by the DUV laser via a “head-to-head” direction, which provided sufficient overlap between the DUV laser and the molecular beam in order to maximize the ionic abundance for mass spectrometer. The molecular density of D2O (ρ, molecule/m3) in the reaction tube was controlled by varying the on-time pulse width
of the reaction gas injection. The value of ρ in this study were estimated to be 0.5~1.8×1019
molecule/m3, and the corresponding partial pressure (P) of reaction gas was 20~75 mPa for the
different valve-opening times.
1.2 Theoretical Methods
All electronic structure computations were conducted to understand the nature of hydrogen liberation in the reaction V clusters with water in selected cases. he structure of charged vanadium clusters have been experimentally measured using the IR-MPD8-9, photoelectron
spectroscopy (PES)10, and collision-induced dissociation (CID)11 methods.12 As for the neutral
species, the disordered structures of the Vn clusters (n = 2–17, 55, 147 and 309) have been
performed by molecular-dynamics (MD) simulations13 and the electronic structures of V n
clusters (n = 2–13) have being discussed by DFT methods.14
The global research of V10, V13, and V16 was based on ab initio evolutionary algorithm
USPEX (Universal Structure Predictor: Evolutionary Xtallography)15 combined with Vienna
Structures and relative energies of reaction products and transition states as well as Vn
(n=4-17) isomers were optimized without symmetry restriction at BPW91/TZVP level of theory. The orbital analysis of Vn clusters are conducted at B3LYP21-22/TZVP level. Frequency calculations
were performed at the same level to confirm the nature of the stationary structures, and meanwhile to evaluate the zero-point correction energies (ZPE).
Searches of different energetically viable reaction paths also took Intrinsic reaction coordinate (IRC) into consideration to ensure that each transition state (TS) correctly connects the reactant and the product minima. Adiabatic ionization potential, vertical ionization potential, Hirshfeld charge and surface electrostatic potential were calculated at the BPW91/TZVP level. In addition, considering that small metal clusters are possibly to carry certain magnetic moment23-24, the magnetic moment for vanadium clusters are double checked using VASP
software, in which the generalized gradient approximation (GGA)25 in the
Perdew−Burke−Ernzerhof (PBE)26 form and a cutoff energy of 550 eV for plane wave basis set
were adopted. The ionic convergence limit was set to 0.02 eV Å−1, while the electronic
convergence limit was set to 10−6 eV. Graphical structures are presented using the Gaussview
and VMD27. All orbitals and surface electrostatic potentials were plotted using the Multiwfn28
and VMD.
Table S1 shows the calculated bond dissociation energy, bond distance and frequency. BPW91/TZVP finds an optimized bond length of 1.763 Å for V2 cluster, which is consistent
with the experimental value 1.774 Å. Also, the calculated bond dissociation energy of BPW91 is the closest to the experimental result. Moreover, BPW91 produced water bending frequency for the V3+-H2O is 1621 cm-1, which is in good accord with the experimental value 1622 cm-1
(Show in table 2). These results support the selection of BPW91 method for the analysis of Vn
clusters and reaction between Vn and water molecules.
In order to search stable structures of Vn (n=2-17) clusters, we built the initial structures either
from references or from symmetry structures. The optimized isomers’ structures and relative energies are shown in Figure S5- S9, then we get V10 (D4), V13 (C2v), V16 (C3v). Taking their
symmetric structures into account, we calculate all possible adsorption sites that water may attach to. We also try to put the water hollow sites or bridge sites, while after optimizing the water is still on the atop site. It is accord with the ESP results (Figure S12) that maximum points are located on the atop sites.
Table S1. A comparison of the experimental and theoretical results for the bond dissociation
energy (D), bond distance (d) and harmonic frequency () for V2.
Method D(eV) d(Å) (cm-1) Ref.
LSD 3.85 1.746 594 ref29
BPW91/TZVP 2.98 1.763 654 This work
BP86/TZVP 3.58 1.760 659 This work
PBE/TZVP 3.41 1.761 655 This work
B3LYP/TZVP 1.24 1.733 709 This work
TPSS/TZVP 3.00 1.764 658 This work
Experiment 2.75 1.774 535 ref30
Table S2. A comparison of the experimental and theoretical results for the vibration frequency
in V3+-H2O.
Method (cm-1) Ref.
BPW91/TZVP 1621 This work
BP86/TZVP 1612 This work
PBE/TZVP 1613 This work
B3LYP/TZVP 1653 This work
TPSS/TZVP 1651 This work
S2. Supplementary Experiments
Figure S1. Mass spectra of (a) neutral Vn (n=1-40) clusters and (b-d) Vn reacting with different amounts of D2O with the partial pressures of D2O vapor
Figure S2. Mass Spectra of (a) neutral Vn (n=1-35) clusters and (b-c) Vn reacting with different amount of H218O. The partial pressures of H218O vapor
Figure S3. (a) Mass Spectra of neutral Vn (n=1-41) clusters and after reacting with different amount of He. The partial pressures of pure He in the reaction tube are estimated to be ~1.5 Pa and ~2.0 Pa respectively. (b) Mass Spectra of neutral Vn (n=1-29) clusters and after reacting with different
Figure S4. Mass Spectra of the neutral Vn (n=1-40) clusters and after reacting with different amount of CO2. The partial pressures of reactants (20% in He) in the reaction tube are estimated
S3. Structures and Energetics of V
nFigure S5. (a) The global research of neutral V10 based on USPEX combined with VASP. The energies are relative to the global minimum structure. The evolutionary simulation used 20 structures per generation. Besides, the lowest-energy structure of the previous generation survived into the next generation. The structures with relative lower energies are labelled by Isomer A, B, and C. (b) Optimized isomers and relative zero-point energies (eV) of neutral V16
Figure S6. (a) The global research of neutral V13 based on USPEX combined with VASP. The energies are relative to the global minimum structure. The evolutionary simulation used 20 structures per generation. Besides, the lowest-energy structure of the previous generation survived into the next generation. The structures with relative lower energies are labelled by Isomer A, B, C, D and E. (b) Optimized isomers and relative zero-point energies (eV) of neutral V16 with structures A-E as initial guess calculated at BPW91/TZVP level using G09 grogram.
Figure S7. (a) The global research of neutral V16 based on USPEX combined with VASP. The energies are relative to the global minimum structure. The evolutionary simulation used 20 structures per generation. Besides, the lowest-energy structure of the previous generation survived into the next generation. The structures with relative lower energies are labelled by isomer A, B, C and D. (b) Optimized isomers and relative zero-point energies (eV) of neutral V16 with structures A-D as initial guess calculated at BPW91/TZVP level using G09 grogram.
Figure S8. Optimized lowest energy structures of the neutral Vn (n=2-17) clusters and their isomers, with relative energies in eV. M indicates spin multiplicity.
Figure S9. The ground state structure of Vn (n=2-17) clusters with point group, electronic state and magnetic moment determined. The bond lengths are labelled in blue and given in Å.
Figure S10. Unpaired electron spin density of Vn and VnH2O, with the isosurface value at
Figure S11. Calculated electronic affinity (EA, eV) of the neutral vanadium clusters at
BPW91/TZVP level.
S4. Partial Charges and Frontier Orbitals
Figure S12. Hirshfeld charge and surface electrostatic potential of a) V10, b) V13, c) V15 and d)
Figure S14. Partial density of states (PDOS) and selected canonical molecular orbitals (CMOs)
of neutral (a) V10, (b) V13, (c) V16 clusters calculated at BPW91/TZVP level. The orange, blue,
S5. V
nH
2O Clusters
Figure S15. (a) Binding energy (eV) of Vn-H2O calculated at BPW91/ TZVP level of theory. (b) The low-lying energy structures of VnH2O clusters.
Figure S16. Optimized isomers of neutral Vn-H2O (n=10,13,16) with relative energies in eV.
Table S3. Binding energy (eV) of Vn-H2O, bond length and Mayer bond order of V-O bond in
VnH2O (n=10, 13, 16) clusters calculated at BPW91/ TZVP level of theory.
Binding energy (eV) Bond length Mayer bond order
V10H2O 0.61 2.191 0.21
V13H2O 0.70 2.181 0.25
V16H2O 0.35 2.194 0.21
Table S4. Energy decomposition analysis (EDA) results for VnH2O (n=10, 13, 16) at the
B3LYP-D3BJ/TZP level, taking Vn and H2O as interacting fragments. Energy values are given
in kcal/mol. Complex Total Bonding Energy ΔEtot Electrostatic Interaction ΔEelstat Pauli Repulsion ΔEpauli Orbital Interactions ΔEorb V10H2O -17.96 -42.70 44.62 -16.04 V13H2O -19.79 -47.72 50.82 -18.81 V16H2O -18.44 -43.51 45.70 -16.63
Table S5. Vertical ionization energy (VIE, eV) of neutral VnH2O and VnO clusters calculated
at BPW91/ TZVP level of theory.
cluster VIE (eV) cluster VIE (eV)
V1H2O 6.40 V1O 7.41 V2H2O 5.79 V2O 6.39 V3H2O 5.76 V3O 5.62 V10H2O 4.91 V10O 5.10 V13H2O 4.50 V13O 4.75 V16H2O 4.51 V16O 4.76
Figure S17. (a-c) Natural population analysis (NPA) charge (q/|e|) on vanadium and oxygen
atoms in VnH2O (n=10, 13, 16) clusters. (d-e) NPA charge on hydrogen atoms in HV13OH
(structure F and L in Figure 5). The calculation are conducted at BPW91/TZVP level using NBO6.0 method32 (details in Table S6).
Table S6. Natural atomic charges (q/|e|) and electronic configurations of VnH2O (n=10, 13, 16)
and HV13OH calculated at BPW91/ TZVP level of theory using NBO6.0 method.
Atom and Number
Atomic
Charges q Electronic Configurations
V10H2O (1A) V 1 V 2 V 3 V 4 V 5 V 6 V 7 V 8 V 9 V 10 O 11 H 12 H 13 -0.02424 -0.09487 -0.01300 -0.01893 -0.01062 0.00374 0.00446 -0.00427 0.01018 0.02644 -0.86471 0.49352 0.49232 [Ar]4s(0.83)3d(4.18)4p(0.03)5s(0.01)4d(0.01) [Ar]4s(0.75)3d(4.32)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.82)3d(4.18)4p(0.03)5s(0.01)4d(0.01) [Ar]4s(0.81)3d(4.19)4p(0.03)5s(0.01)4d(0.01) [Ar]4s(0.81)3d(4.19)4p(0.03)5s(0.01)4d(0.01) [Ar]4s(0.81)3d(4.18)4p(0.03)5s(0.01)4d(0.01) [Ar]4s(0.82)3d(4.17)4p(0.03)4d(0.02) [Ar]4s(0.81)3d(4.18)4p(0.03)4d(0.01) [Ar]4s(0.85)3d(4.14)4p(0.02)4d(0.01) [Ar]4s(0.82)3d(4.15)4p(0.02)4d(0.01) [He]2s(1.73)2p(5.12)3p(0.01)3d(0.01) 1s(0.50) 1s(0.50) V13H2O (2A) V 1 V 2 V 3 V 4 V 5 V 6 V 7 V 8 V 9 V 10 V 11 V 12 V 13 O 14 H 15 H 16 -0.70156 0.07018 -0.03961 0.09623 0.08316 0.11497 0.02135 0.07888 0.01972 -0.03732 0.00995 0.08815 0.08938 -0.87238 0.48613 0.49278 [Ar]4s(0.77)3d(4.86)4p(0.04)4d(0.06) [Ar]4s(0.82)3d(4.08)4p(0.03)4d(0.02) [Ar]4s(0.94)3d(4.07)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.81)3d(4.07)4p(0.03)4d(0.02) [Ar]4s(0.98)3d(3.92)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.88)3d(3.98)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.89)3d(4.07)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.99)3d(3.90)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.73)3d(4.21)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.96)3d(4.05)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.89)3d(4.08)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.91)3d(3.98)4p(0.03)5s(0.01)4d(0.02) [Ar]4s(0.81)3d(4.08)4p(0.03)4d(0.02) [He]2s(1.73)2p(5.12)3p(0.01)3d(0.01) 1s(0.50)2s(0.01) 1s(0.50)
V16H2O (1A) V 1 V 2 V 3 V 4 V 5 V 6 V 7 V 8 V 9 V 10 V 11 V 12 V 13 V 14 V 15 V 16 O 17 H 18 H 19 -0.01644 0.05964 -0.56464 -0.00934 0.07107 0.01854 0.00736 0.04962 0.07292 0.03797 0.09023 0.03850 0.06204 -0.00835 -0.06536 0.03260 -0.87058 0.49717 0.49702 [Ar]4s(0.82)3d(4.19)4p(0.03)4d(0.02) [Ar]4s(0.80)3d(4.12)4p(0.02)4d(0.02) [Ar]4s(0.75)3d(4.72)4p(0.07)4d(0.04) [Ar]4s(0.87)3d(4.12)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.71)3d(4.22)4p(0.02)4d(0.02) [Ar]4s(0.85)3d(4.11)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.84)3d(4.12)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.82)3d(4.12)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.71)3d(4.21)4p(0.02)4d(0.02) [Ar]4s(0.86)3d(4.08)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.71)3d(4.19)4p(0.03)4d(0.02) [Ar]4s(0.86)3d(4.09)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.81)3d(4.11)4p(0.02)5s(0.01)4d(0.02) [Ar]4s(0.82)3d(4.18)4p(0.03)4d(0.02) [Ar]4s(0.74)3d(4.31)4p(0.03)5s(0.01)4d(0.03) [Ar]4s(0.86)3d(4.09)4p(0.02)5s(0.01)4d(0.02) [He]2s(1.72)2p(5.13)3p(0.01)3d(0.01) 1s(0.50) 1s(0.50) HV13OH (2A, structure F in Figure 5b) V 1 V 2 V 3 V 4 V 5 V 6 V 7 V 8 V 9 V 10 V 11 V 12 V 13 O 14 H 15 H 16 -0.57519 0.11869 -0.05322 0.00620 0.10370 0.24199 0.05615 0.29484 0.32000 0.00492 -0.02132 0.09469 0.10440 -0.87681 -0.28786 0.46880 [Ar]4s( 0.82)3d( 4.69)4p( 0.04)4d( 0.04) [Ar]4s( 0.65)3d( 4.20)4p( 0.03)4d( 0.02) [Ar]4s( 0.85)3d( 4.18)4p( 0.03)4d( 0.02) [Ar]4s( 0.79)3d( 4.17)4p( 0.03)4d( 0.02) [Ar]4s( 0.92)3d( 3.96)4p( 0.03)4d( 0.02) [Ar]4s( 0.83)3d( 3.90)4p( 0.03)4d( 0.02) [Ar]4s( 0.75)3d( 4.18)4p( 0.03)4d( 0.02) [Ar]4s( 0.72)3d( 3.96)4p( 0.03)4d( 0.02) [Ar]4s( 0.55)3d( 4.08)4p( 0.04)5s( 0.01)4d( 0.03 ) [Ar]4s( 0.88)3d( 4.09)4p( 0.03)4d( 0.02) [Ar]4s( 0.86)3d( 4.14)4p( 0.03)5s( 0.01)4d( 0.02 ) [Ar]4s( 0.80)3d( 4.07)4p( 0.03)4d( 0.02) [Ar]4s( 0.79)3d( 4.08)4p( 0.03)4d( 0.02) [He]2s( 1.76)2p( 5.10)3p( 0.01) 1s( 1.28) 1s( 0.53) HV13OH (2A, structure M in Figure 5b) V 1 V 2 V 3 V 4 V 5 V 6 V 7 V 8 V 9 V 10 V 11 V 12 V 13 -0.62816 0.26359 -0.05024 0.03069 0.09126 0.15424 0.04465 0.28653 0.21753 0.13383 -0.02348 0.18981 0.09586 [Ar]4s( 0.81)3d( 4.76)4p( 0.04)4d( 0.04) [Ar]4s( 0.49)3d( 4.20)4p( 0.03)4d( 0.03) [Ar]4s( 0.88)3d( 4.16)4p( 0.02)4d( 0.02) [Ar]4s( 0.76)3d( 4.19)4p( 0.03)4d( 0.02) [Ar]4s( 0.98)3d( 3.91)4p( 0.03)4d( 0.02) [Ar]4s( 0.95)3d( 3.87)4p( 0.03)4d( 0.02) [Ar]4s( 0.79)3d( 4.14)4p( 0.04)4d( 0.02) [Ar]4s( 0.73)3d( 3.97)4p( 0.03)4d( 0.02) [Ar]4s( 0.65)3d( 4.09)4p( 0.03)4d( 0.02) [Ar]4s( 0.77)3d( 4.07)4p( 0.02)4d( 0.02) [Ar]4s( 0.91)3d( 4.09)4p( 0.03)5s( 0.01)4d( 0.02 ) [Ar]4s( 0.64)3d( 4.15)4p( 0.03)4d( 0.02) [Ar]4s( 0.75)3d( 4.13)4p( 0.03)4d( 0.02)
S6. Hydrogen Evolution Reaction
Figure S18. HOMO and LUMO orbitals of Vn, VnH2O, and VnO (n=10, 13, 16).
Figure S19. The zero-point-vibration corrected total energies of the hydrogen evolution
reaction (∆𝒓𝐻0, red dots) and Gibbs free energy (ΔG, blue square) of Vn (n=1-16) with H2O,
where the values are just shifted with the same energy determined by the H2O reactant and H2
Figure S20. Reaction pathways for hydrogen evolution in the reaction of V1, V2 and V3 with
water. The energy values are relative to the entrance channel, corrected with zero-point vibration energies, and given in eV.
Figure S21. Reaction pathways for hydrogen evolution in the reaction of V10 with water. The energy values are relative to the entrance channel, corrected with zero-point vibration energies, and given in eV. Inserts are the lowest unoccupied molecular orbital (LUMO) and surface electrostatic potential (ESP) of V10. Structure B-O is the optimized structure of intermediates
and transition states.
Figure S22. Reaction pathways for hydrogen evolution in the reaction of V16 with water. The energy values are relative to the entrance channel, corrected with zero-point vibration energies, and given in eV. Inserts are the lowest unoccupied molecular orbital (LUMO) and surface electrostatic potential (ESP) of V16. Structure B-M is the optimized structure of intermediates
and transition states.
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