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Electron Detachments of NbSin−/0 (n = 1−3) Clusters from Density

Matrix Renormalization Group-CASPT2 Calculations
Van Tan Tran*
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ABSTRACT: The electronic states of NbSin−/0/+ (n = 1−3) clusters

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have been explored using the state-of-the-art DMRG-CASPT2 method

with relatively large active spaces. The leading configurations, bond
distances, vibrational frequencies, and relative energies of the low-lying
states were identified. Electron detachment energies of the anionic
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cluster and ionization energies of the neutral clusters were reported at

the DMRG-CASPT2 level. The ground states of the NbSin−/0/+ (n =
1−3) clusters were predicted as the 3Δ, 4Π, and 5Π states of the linear
NbSi−/0/+, the 3A2, 4B1, and 3B1 states of cyclic NbSi2−/0/+, and the 1A′,
2
A′, and 3A″ states of tetrahedral NbSi3−/0/+ isomers. The first feature
in the photoelectron spectrum of NbSi− was attributed to the transitions from the anionic 3Δ ground state to the neutral 4Π, 4Δ, and
4
Φ states, whereas the second feature was assigned to the transitions to the neutral 2Δ, 2Σ+, and 2Φ states. The first band in the
photoelectron spectrum of NbSi3− was ascribed to the transition from the anionic 1A′ ground state to the neutral 12A′ and 12A″
states; the second band was attributed to the transitions to 22A′, 22A″, and 32A′ states; and the third band was assigned to the
transition to 32A′ states.

1. INTRODUCTION The resonant two-photon ionization spectrum of the neutral

Transition-metal-doped silicon clusters have been studied to
identify stable structures that can serve as building blocks for
nanomaterials. It has been discovered that a large number of
transition-metal-doped silicon clusters have stable cage
structures.1−9 Both theoretical and experimental methods have
been used to study the structures of silicon clusters doped with
niobium.1,2,10−19 The structure of the neutral diatomic NbSi
cluster was investigated with electron spin resonance spectros-
copy.15 Based on a logical extrapolation of the experimental and
theoretical information on ScO, TiN, VC, YO, ZrN, and NbC,
the ground states of NbSi were assumed to be 2Δ. And this
doublet ground state was considered as quenched in the
matrices and observed in the electron spin resonance spectra.
This investigation focused on the 2Δ, while the other low-lying
electronic states were not explored.
The B3LYP functional calculations using the LANL2DZ
+ECP basis set suggested a 4Φ state as the neutral ground
state.16 The 532 nm photoelectron imaging spectrum of the
NbSi− cluster was reported with two main features at 1.83 and
2.06 eV.17 In the same work, the CCSD(T) and B3LYP
functional calculations, with the LANL2DZ+ECP basis set for
Nb and 6-311++G(3df,3pd) basis set for Si, indicated that the
anionic and neutral ground states were, respectively, 3Δ and 4Δ,
while the neutral first excited state was 4Φ. Based on the
calculated results, two features of the anion photoelectron
spectrum were, respectively, assigned to the transitions from the
anionic 3Δ ground state to the neutral 4Δ and 4Φ states.
NbSi cluster showed a bond dissociation energy of 3.080(3)
eV.18 And the B3LYP functional calculations with the
LANL2DZ+ECP basis set revealed a 6Σ+ as the ground state,
while the 4Π (4Φ), 2Δ, and 2Σ+ were higher in energy by 0.03,
0.16, and 0.59 eV. The CASPT2, CAS-tPBE, and CAS-ftPBE
calculations with ANO-RCC-VTZP basis set and active space of
7 electrons in 10 orbitals showed a ground state of 6Σ+, and the
4
Π state was close in energy at less than 0.1 eV above the ground
state.19 The bond dissociation energies computed with the CAS-
PDFT methods were within 0.26 eV of the experimental value.
Overall, the ground state of the neutral diatomic NbSi clusters
was occasionally specified as the 2Δ, 4Φ, 4Δ, and 6Σ+ states by
different experimental and theoretical methods, whereas the
ground state of the anionic clusters was predicted as 3Δ.
Investigation of the electronic structures of NbSi2−/0/+
clusters using the B3LYP functional and LANL2DZ+ECP
basis set for Nb and 6-311+G(d) basis set for Si revealed the
ground states of 1A1, 2B2, and 1A1 of cyclic isomers.10
Experimental approaches have not been applied to explore the
electronic states of NbSi2−/0/+ clusters. The structures of the
Received: February 22, 2023
Revised: April 25, 2023
Published: May 2, 2023

© 2023 American Chemical Society https://doi.org/10.1021/acs.jpca.3c01230

4086 J. Phys. Chem. A 2023, 127, 4086−4095
The Journal of Physical Chemistry A
NbSi3−/0 clusters were studied with anion photoelectron
spectroscopy.11 The spectrum of the NbSi3− cluster reveals
three bands at 2.28, 3.17, and 3.97 eV. In the same work, the
B3LYP functional with LANL2DZ+ECP basis set for the Nb
and 6-311+G(d) basis set for Si and the CCSD(T) method with
the aug-cc-pVDZ-PP basis set for Nb and cc-pVDZ basis set for
Si were employed to study the structures of NbSi3−/0 clusters.
The computational results showed that the anionic ground state
was 1A1 of a C3v tetrahedral isomer, while the neutral ground
state was a doublet state. The first band in the spectrum was
explained by the transition from the anionic singlet state to the
neutral doublet state. The ground states of NbSi3−/0/+ clusters
were also reported as 1A1 (C3v), 2A′ (Cs), and 3A1 (C3v) states of
tetrahedral isomers by the B3LYP functional calculation with the
LANL2DZ+ECP basis set for Nb and the 6-311+G(d) basis set
for Si.10
In this work, we investigate the electron states of NbSin−/0/+ (n
= 1−3) clusters using density functional theory (DFT),
CASPT2, and the DMRG-CASPT2 methods. With an ability
to expand the active space to around 28 orbitals, the DMRG-
CASPT2 method is known as an appropriate method for
determining the energies of the electronic states of transition-
metal-containing compounds.20−29 The DMRG-CASPT2 cal-
culations are expected to provide highly accurate energies for all
the relevant electronic states of NbSin−/0/+ (n = 1−3) clusters.
Electron detachment energies are estimated for the anionic and
neutral clusters. And the computational findings are then
utilized to analyze the available anion photoelectron spectra.
2. COMPUTATIONAL DETAILS
The initial geometries of the relevant isomers were obtained
from the previous studies as shown in Figure 1.10,11 In particular,
Figure 1. Structures and symmetries of NbSin−/0/+ (n = 1−3) clusters.
NbSi2−/0/+ clusters have a cyclic structure with C2v symmetry,
while NbSi3−/0/+ clusters exhibit a tetrahedral structure with C3v
or Cs symmetry. For computational convenience, all calculations
for the tetrahedral structure of NbSi3−/0/+ clusters used Cs
symmetry. To optimize the geometries and determine the
harmonic vibrational frequencies of the electronic states of the
NbSi2−/0/+ and NbSi3−/0/+ clusters, we employed the BP86
functional, and the def2-QZVP basis set was employed. It should
be noted that the def2-QZVP basis set includes an effective core
potential of 28 electrons for niobium. The NWCHEM 7.0.2
4087
pubs.acs.org/JPCA Article
software package was used to perform DFT calculations. The
multidimensional Franck−Condon factors of the electron
detachments of the anionic clusters were simulated by using
the MOLFC code based on the BP86 geometries and vibrational
normal modes.30,31 The Mayer bond order of the electronic
states was computed using the Multiwfn 3.7 package32 based on
the Kohn−Sham DFT wave function.
The CASPT2 and DMRG-CASPT2 calculations used the
ANO-RCC-VQZP basis sets for niobium and silicon.33,34 The
scalar relativistic effects were included by using the Douglas-
Kroll-Hess transformation of one-electron integrals.35,36 The
empirical correction applied to the zeroth-order Hamiltonian
(IPEA) and imaginary shifts were set to be 0.25 and 0.10,
respectively. Electrons in the 1s, 2s, 2p, 3s, 3p, and 3d orbitals of
Nb and the 1s orbital of Si were frozen. The CASPT2 approach
was used to create potential energy profiles of NbSi−/0/+,
optimize the geometries of NbSi2−/0/+, and determine the single-
point energies of NbSi3−/0/+ clusters. The DMRG-CASPT2
method was utilized to compute the single-point energies of the
electronic states of NbSin−/0/+ (n = 1−3) clusters. The CASPT2
and DMRG-CASPT2 calculations were performed using
OpenMolcas37 and CheMPS2,38 respectively.
To generate the wave functions for the CASPT2 and DMRG-
CASPT2, CASSCF and DMRG-CASSCF were used. For the
diatomic NbSi−/0/+ clusters, the active spaces of CASSCF
calculations were chosen to include the 4d and 5s orbitals of Nb
and the 3s, 3p, and 3d orbitals of Si. The resulting active space
has 10, 9, or 8 electrons distributed in 15 orbitals and is known as
(10e, 9e, 8e; 15o). The active space of DMRG-CASSCF for
these diatomic clusters was enlarged to 26 orbitals by adding the
4f, 5p, and 6s orbitals of Nb to the CASSCF active space. This
DMRG-CASSCF active space is known as (10e, 9e, 8e; 26o).
For NbSi2−/0/+ clusters, the CASSCF active space (14e, 13e,
12e; 14o) was composed of the 4d and 5s orbitals of niobium
and 3s and 3p orbitals of silicon. The DMRG-CASSCF active
space (14e, 13e, 12e; 27o) of NbSi2−/0/+ clusters was produced
by combining the 5p orbitals of niobium and 3d orbitals of
silicon with the CASSCF active space. For NbSi3−/0/+ clusters,
the CASSCF active space (12e, 11e, 10e; 15o) comprised the 4d
and 5s orbitals of niobium and the 3p orbitals of silicon. The
DMRG-CASSCF active space (18e, 17e, 16e; 18o) of
NbSi3−/0/+ clusters was created by adding the 3s orbitals of
silicon to the CASSCF active space. The 15 3d orbitals of Si were
not included in the active space of NbSi3−/0/+ clusters because
the current computer and software can conduct a DMRG-
CASPT2 calculation with an active space of roughly 28 orbitals.
In general, the CASSCF active space of NbSin−/0/+ (n = 1−3)
clusters contains 15, 14, and 15 orbitals, whereas the
corresponding DMRG-CASSCF active spaces possess 26, 27,
and 18 orbitals.
3. RESULTS AND DISCUSSION
3.1. NbSi−/0/+. Table 1 shows the computational results of
the electronic states of the NbSi−/0/+ clusters. The CASPT2 and
DMRG-CASPT2 relative energies correspond to each other for
most of the electronic states. Using the CASPT2 method, we
investigated the spin−orbit state interaction among the
electronic states of NbSi−/0/+ clusters. Our findings indicate
that the energy relaxations caused by spin−orbit coupling range
from −0.15 to −0.05 eV. These energy relaxations are small and
therefore can not change the CASPT2 and DMRG-CASPT2
relative energy order of the electronic states. The ground state of
the anionic cluster is 13Δ, whereas the excited states are 1Σ+, 5Π,
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Table 1. Leading Configurations, Bond Lengths, Harmonic Vibrational Frequencies, and Relative Energies of the Relevant
Electronic States of NbSi−/0/+ Clusters
relative energy (eV)
a a −1 b
state leading configuration Nb−Si (r) (Å) frequency (cm ) CASPT2 DMRG-CASPT2c
−
NbSi (C∞v)
13Δ 12σ213σ214σ16π47π02δ1 2.310 418 0.00 0.00
13Δ1 −0.09
13Δ2 −0.04
13Δ3 0.01
1 +
Σ 12σ213σ214σ26π47π02δ0 2.261 447 0.12 0.22
5
Π 12σ213σ214σ16π37π02δ2 2.381 385 0.34 0.39
3
Φ 12σ213σ214σ26π37π02δ1 2.322 511 0.41 0.47
23Δ 12σ213σ114σ26π47π02δ1 2.248 430 0.70 0.84
5 −
Σ 12σ213σ214σ16π37π12δ1 2.437 303 0.90 0.94
NbSi (C∞v)
4
Π 12σ213σ214σ16π37π02δ1 2.343 411 0.00 0.00
4
Π1/2 −0.07
4
Π3/2 −0.01
4
Π5/2 0.05
4
Δ 12σ213σ114σ16π47π02δ1 2.229 453 0.11 0.12
4
Δ1/2 −0.04
4
Δ3/2 −0.01
4
Δ5/2 0.03
4
Δ7/2 0.07
4
Φ 12σ213σ214σ16π37π02δ1 2.347 407 0.08 0.15
4
Φ3/2 0.03
4
Φ5/2 0.06
4
Φ7/2 0.08
4
Φ9/2 0.12
6 +
Σ 12σ213σ214σ16π27π02δ2 2.431 381 0.17 0.23
2
Δ 12σ213σ214σ06π47π02δ1 2.293 421 0.35 0.31
2 +
Σ 12σ213σ214σ16π47π02δ0 2.245 473 0.41 0.40
2
Φ 12σ213σ214σ16π37π02δ1 2.351 415 0.38 0.48
2
Π 12σ213σ214σ26π37π02δ0 2.349 427 0.59 0.79
NbSi+ (C∞v)
5
Π 12σ213σ114σ06π37π02δ2 2.326 399 0.00 0.00
5
Π1 −0.05
5
Π2 −0.03
5
Π3 0.00
3
Δ 12σ213σ114σ06π47π02δ1 2.208 464 −0.06 0.08
3
Δ1 −0.16
3
Δ2 −0.13
3
Δ3 −0.05
3
Φ 12σ213σ214σ06π37π02δ1 2.323 395 0.10 0.22
5
Δ 12σ213σ214σ16π27π02δ1 2.469 353 0.19 0.40
1 +
Σ 12σ213σ214σ06π47π02δ0 2.208 439 0.38 0.56
a
Bond lengths and vibrational frequencies are estimated at the CASPT2 level by fitting the potential energy profiles to a fourth-degree polynomial
curve. bActive space (10e, 9e, 8e; 15o). cSingle-point energy calculations with an active space of (10e, 9e, 8e; 26o) based on the structures
optimized with the CASPT2 method.
3
Φ, 23Δ, and 5Σ−. Previous calculations using the B3LYP Nb, while the 2δ orbitals are primarily composed of the 4dx2−y2
functional and CCSD(T) methods also suggest a 3Δ state as the and 4dxy orbitals of Nb. Because the bonding 12σ, 13σ, and 6π
anionic ground state.16,17 Figure 2 depicts the molecular orbitals orbitals are fully occupied and the mostly nonbonding 14σ and
and electron occupation numbers of the triplet ground state. 2δ orbitals are singly occupied, the Mayer bond of the 13Δ
The bonding orbitals are specified as 12σ (resulting from the ground state is computed to be 4.14.
interaction between the 3dz2 orbital of Nb and the 3s orbital of The ground state of the neutral cluster is 4Π, and the excited
Si), 13σ (resulting from the combination of the 4dz2 orbital of states are 4Δ, 4Φ, 6Σ+, 2Δ, 2Σ+, 2Φ, and 2Π. In comparison to the
Nb and the 3pz orbital of Si), and 6π (arising from the bonding anionic 3Δ ground state, the neutral quartet ground state lacks
between the 4dxz and 4dyz orbitals of Nb and the 3px, 3py orbitals one electron in the bonding 6π orbitals. As a result, the Nb−Si
of Si). The 14σ orbital is mainly composed of the 5s orbital of bond length elongates from 2.310 Å in the anionic triplet state to
4088 https://doi.org/10.1021/acs.jpca.3c01230
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Using DMRG-CASPT2 electron detachment energies, we

propose a new assignment for the photoelectron spectrum of
NbSi−. The unresolved wide bands X and A in the spectrum are
believed to be the result of several electron detachment
processes. Table 2 presents the electron detachment energies

Table 2. Adiabatic and Vertical Detachment Energies (ADEs

and VDEs) of NbSi− and Adiabatic and Vertical Ionization
Energies (AIEs and VIEs) of NbSi Clusters As Computed at
the DMRG-CASPT2 Level
ADE (AIE) VDE (VIE)
(eV) (eV)
DMRG- DMRG-
cluster transition orbital CASPT2a expt.b CASPT2a expt.b
−/0 3 4
NbSi Δ→ Π 6π 1.59 1.58 1.61 1.83
3
Δ → 4Δ 13σ 1.71 1.58 1.76 1.83
3
Δ → 4Φ 6π 1.74 1.58 1.75 1.83
3
Δ → 2Δ 14σ 1.90 1.91 2.06
3
Δ → 2Σ+ 2δ 1.98 2.02 2.06
3
Δ → 2Φ 6π 2.07 2.08 2.06
NbSi0/+ 4
Π → 5Π 6.77 6.77
Figure 2. Relevant molecular orbitals and occupation numbers of the 4
Π → 3Δ 6.85 6.98
3
Δ ground state of NbSi− cluster as obtained from the CASSCF 4
Π → 3Φ 14σ 6.99 6.99
calculation. a
Active space (10e, 9e, 8e; 26o). bRef 17. The uncertainties of the
experimental detachment energies are ±0.03 eV.

2.343 Å in the neutral quartet state. Also, the Mayer bond order
decreases from 4.14 in the anionic triplet state to 3.56 in the
neutral quartet state. Our finding agrees with the previous
CASSCF calculations in which the 4Π is predicted as the ground
state.19 However, our results differ from the previous
calculations in which the neutral ground state is predicted as
the 4Δ state17 by the B3LYP functional and 6Σ+ state19 by the
CASPT2, CAS-tPBE, and CAS-ftPBE methods. Otherwise, our
results point out that the 2Δ state is the neutral excited state with
a relative energy of 0.31 eV, but the electron spin resonance
spectra indicate this doublet state as the neutral ground state.15
In the case of the cationic cluster, the CASPT2 and DMRG-
CASPT2 give different relative energies for 5Π and 3Δ states.
The CASPT2 method predicts the triplet state as the ground
state, while DMRG-CASPT2 favors the quintet state. The
energy differences between these two states as determined by
the CASPT2 and DMRG-CASPT2 methods are, respectively,
−0.06 and 0.08 eV. Because the DMRG-CASPT2 uses a larger
active space, we believe the ground state of the cationic cluster is
the 5Π. The Mayer bond orders of these quintet and triplet states
are computed to be 3.17 and 3.67. The previous B3LYP
functional calculations predict a different result in which the 3Δ
is identified as the cationic ground state, while the quintet state
and other excited states are not mentioned.16
The 532 nm photoelectron spectrum of NbSi− as presented in
Figure 4 exhibited X and A features at 1.83 and 2.06 eV in a
previous study.17 The anisotropy parameter β of 1.4(1) of the X
band indicates an electron detachment from an σ orbital. In the
same work, based on the time-dependent B3LYP functional
calculations, the X feature was assigned to the transition from the
anionic 3Δ ground state to the neutral 4Δ ground state, and the A
feature was ascribed to the transition to the neutral excited 4Φ
state. The adiabatic detachment energy (ADE) of the transition
to the 4Δ state was evaluated to be 1.571 eV, while the vertical
detachment energies (VDEs) of the transitions to the 4Δ and 4Φ
states were estimated to be 1.672 and 1.931 eV, respectively.
4089
of the anionic and neutral diatomic clusters. The VDEs of
transitions from the anionic 3Δ ground state to the neutral 4Π,
4
Δ, and 4Φ states are 1.61, 1.76, and 1.75 eV, respectively. In
principle, the computed VDEs correspond to the experimental
value of 1.83 ± 0.03 eV for the X feature. These transitions
involve the removal of electrons from the 6π, 13σ, and 6π
orbitals, explaining the anisotropy parameter value of 1.4(1) for
the X band. The calculated ADE of 1.59 eV for the transition to
4
Π agrees well with the experimental value of 1.58 (±0.03) eV of
the X band. Franck−Condon factors of transitions from the
anionic 3Δ state to the neutral 4Π, 4Φ, and 4Δ states are
displayed in Figures 3a, 3b, and 3c, respectively. The results
show that transitions to the 4Π and 4Φ states have less
vibrational progression than the transition to the 4Δ state due to
the relaxation of the Nb−Si bond being less in the former
transitions. As can be seen in Table 1, the Nb−Si bond increases
from 2.310 Å to 2.343 and 2.347 Å in the transition from 3Δ to
4
Π and 4Φ states and reduces to 2.229 Å in the transition to the
4
Δstate. The A feature in the spectrum (Figure 4) can be
explained by three transitions to the neutral excited 2Δ, 2Σ+, and
2
Φ states, involving the removal of electrons from the 14σ, 2δ,
and 6π orbitals, respectively. The evaluated VDEs of 1.91, 2.02,
and 2.08 eV of these transitions are consistent with the
experimental value of 2.06 (±0.03) eV. In general, we assign the
transitions to 4Π, 4Δ, and 4Φ states to the X band and the
transitions to 2Δ, 2Σ+, and 2Φ states to the A band. Higher-
resolution spectroscopy is necessary to resolve the fine
structures of the bands.
Within the NbSi0/+ clusters, the transitions from the neutral
4
Π ground state to the cationic 5Π, 3Δ, and 3Φ states have
adiabatic ionization energies (AIEs) of 6.77, 6.85, and 6.99 eV
and vertical ionization energies (VIEs) of 6.77, 6.98, and 6.99
eV. It should be noted that, in the transitions to the 5Π, 3Δ, and
3
Φ, only the transition to the 3Φ is a one-electron detachment
process in which one electron is removed from the 14σ orbital.
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Figure 3. Vibrational progressions of the 3Δ → 4Π transition of NbSi−/0 clusters (a), the 3Δ → 4Φ transition of NbSi−/0 clusters (b), the 3Δ → 4Δ
transition of NbSi−/0 clusters (c), the 3A2 → 4B1 transition of NbSi2−/0 clusters (d), and the 1A′ → 12A′ and 1A′ → 12A″ transitions of NbSi3−/0 clusters
(e, f) as obtained from the Franck−Condon factor simulations.

3.2. NbSi2−/0/+. Table 3 presents the calculated bond
distances and relative energies of the electronic states of
NbSi2−/0/+ clusters. The results show that the relative energies of
the CASPT2 method correspond with those of the DMRG-
CASPT2 method. In several cases, the CASPT2 method inverts
the energy order of the electronic states as compared to the
DMRG-CASPT2 method. At the DMRG-CASPT2 level, the
anionic ground state is 3A2, whereas the excited states are 5A1,
1
A1, 5B1, 3B1, and 3B2. The Mayer bond order of Nb−Si and Si−
Si bonds of 3A2 are estimated to be 2.99 and 1.52. Figure 5
depicts the molecular orbitals and electron occupation numbers
4090
of the anionic triplet ground state. It can be seen from the figure
that the 6b1 and 10b2 orbitals are fully occupied, while the 17a1
and 3a2 orbitals are all singly occupied.
The neutral ground state is specified as 4B1, and the excited
states are predicted as 2A1, 2A2, and 2B2. As compared to the
anionic 3A2 ground state, the 4B1 state has one fewer electron in
the 10b2 orbital. The 10b2 is the bonding orbital of 4dyz of Nb
with πy (3py) antibonding orbital of Si2 moiety. Therefore, the
Nb−Si bond elongates from 2.365 to 2.397 Å and the Si−Si
bond shortens from 2.386 to 2.265 Å in the transition from 3A2
to 4B1 states. The Mayer bond orders of Nb−Si decrease from
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Table 3. Leading Configurations, Bond Lengths, and Relative

Energies of the Electronic States of NbSi2−/0/+ Clusters
relative energy (eV)
Nb−Si (r1),
Si−Si (r2) DMRG-
state leading configuration (Å)a CASPT2b CASPT2c
NbSi2−
(C2v)
3
A2 16a1217a1118a106b127b10 2.365, 0.00 0.00
2.387
Figure 4. Photoelectron spectrum of NbSi− as recorded with photon 9b2210b2211b203a21
5
energy of 532 nm.17 The blue and red lines represent the calculated A1 16a1217a1118a106b127b11 2.461, 0.69 0.54
2.250
ADEs and VDEs, respectively. Reproduced with permission from ref 17.
Copyright 2013 Royal Society of Chemistry. 9b2210b2111b203a21
1
A1 16a1217a1218a106b127b10 2.308, 0.78 0.59
2.542
2.99 to 2.43, while that of Si−Si increases from 1.52 to 1.71 in 9b2210b2211b203a20
the transition from the 3A2 to 4B1 states. As a result of the strong 5
B1 16a1217a1118a116b127b10 2.477, 0.79 0.66
structural relaxation, the Franck−Condon factor simulation for 2.272
the 3A2 → 4B1 transition in Figure 3c shows extensive vibrational 9b2210b2111b203a21
progression with frequencies of 316 and 480 cm−1. Table 4 3
B1 16a1217a1218a106b127b10 2.439, 0.81 0.67
2.249
shows the electron detachment energies of the transitions from
9b2210b2111b203a21
the anionic to the neutral cluster. The VDEs of transitions to 4B1, 3
2 B2 16a1217a1118a106b127b10 2.345, 0.99 0.77
A2, 2A1, and 4B2 are 1.64, 1.83, 1.88, and 2.69 eV, respectively. 2.403
These transitions are accompanied by removing one electron 9b2210b2111b203a22
from the 10b2, 17a1, 3a2, and 5b1 orbitals. The ADE of the NbSi2
transition to the neutral 4B1 ground state is 1.47 eV, as estimated (C2v)
4
with the DMRG-CASPT2 method. B1 16a1217a1118a106b127b10 2.398, 0.00 0.00
In the cationic cluster, 3B1 is the ground state, while the 2.265
excited states are 3B2, 5B1, and 1A1. The Mayer bond orders of 9b2210b2111b203a21
2
Nb−Si and Si−Si bonds of 3B1 are evaluated to be 2.61 and 1.61. A1 16a1217a1118a106b127b10 2.384, 0.38 0.33
2.327
The AIE and VIE of the transitions from the neutral 4B1 state to 9b2210b2211b203a20
the cationic 3B1 state are 6.93 and 6.95 eV, respectively. During 2
A2 16a1217a1018a106b127b10 2.347, 0.32 0.36
the 4B1 → 3B1 transition, one electron is detached from the 17a1 2.382
orbital. Because the 17a1 is almost a nonbonding orbital with the 9b2210b2211b203a21
main contribution of 5s of Nb, the Nb−Si and Si−Si bond 2
B2 16a1217a1018a106b127b10 2.321, 0.61 0.67
lengths slightly relax in the 4B1 → 3B1 transition. 2.376
Our findings differ from the previous B3LYP calculations in 9b2210b2211b203a21
the prediction of the ground states of NbSi2−/0/+ clusters. The NbSi2+
(C2v)
previous B3LYP calculations predicted the 1A1, 2B2, and 1A1 as 3
B1 16a1217a1018a106b127b10 2.381, 0.00 0.00
the anionic, neutral, and cationic ground state,10 whereas our 2.291
CASPT2 and DMRG-CASPT2 calculations prefer the 3A2, 4B1, 9b2210b2111b203a21
and 3B1 states. 3
B2 16a1217a1118a106b127b10 2.426, 0.33 0.23
3.3. NbSi3−/0/+. Table 5 lists the calculated bond distances 2.247
and relative energies of the low-lying states of the NbSi3−/0/+ 9b2210b2111b203a20
5
clusters. The CASPT2 and DMRG-CASPT2 methods provide B1 16a1117a1118a106b127b10 2.361, 0.84 0.62
the same relative energy order for all calculated states. In the 2.444
anionic cluster, the computational results reveal an anionic 9b2210b2111b203a21
1
ground state of 1A′ of a tetrahedral isomer. The anionic singlet A1 16a1217a1218a106b127b10 2.368, 0.72 0.69
2.388
ground state has a Nb−Si (r1, r2) bond length of 2.361 Å and a 9b2210b2011b203a20
Si−Si (r3, r4) bond length of 2.569 Å. The bond orders of Nb− a
Si (r1, r2) bonds are 2.64, while those of Si−Si (r3, r4) bonds are Bond lengths are evaluated with the BP86 functional. bActive space
(14e, 13e, 12e; 14o). cSingle-point energy calculations with an active
1.01. This singlet state exhibits a C3v symmetry and corresponds space of (14e, 13e, 12e; 27o) based on the structures optimized with
to the 1A1 state in the C3v point group. The 3A′ and 3A″ states are the CASPT2 method.
obtained from the singlet ground state by the excitations of an
electron from 28a′ and from 14a″ to 29a′ orbital. As can be seen
in Figure 6, the 28a′ and 14a″ orbitals correspond to the doubly energy splitting of the electronic states of transition-metal-
degenerate E irreducible representations in the C3v point group. doped silicon clusters under the Jahn−Teller effect is known in
Therefore, the 3A′ and 3A″ states are two components of the the 3E (3A′, 3A″) and 2E (2A′, 2A″) states of the tetrahedral
doubly degenerate 3E state in the C3v point group. Under the VSi3−/0.39
Jahn−Teller effect, the degenerate 3E state is unstable and According to the DMRG-CASPT2 method, the ground state
distorts into the 3A′ and 3A″ states in the Cs point group. The of the neutral cluster is determined to be the 2A′ state, with the
2
energies of the 3A′ and 3A″ states are evaluated to be almost the A″ state being only 0.0004 eV higher in energy. These two
same by the CASPT2 and DMRG-CASPT2 methods. The small doublet states are generated from the Jahn−Teller distortion of
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The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Table 5. Leading Configurations, Bond Distances, and

Relative Energies of the Electronic States of NbSi3−/0/+
Clusters
relative energy (eV)
leading Nb−Si (r1, r2), Si− DMRG-
state configuration Si (r3, r4) (Å)a CASPT2b CASPT2b
tetrahedral-NbSi3− (Cs)
1
A′ 27a′228a′229a′0 2.361, 2.361, 0.00 0.00
13a″214a″215a″0 2.569, 2.569
3
A″ 27a′228a′229a′1 2.365, 2.445, 1.31(86) 1.25(08)
13a″214a″115a″0 2.586, 2.413
3
A′ 27a′228a′129a′1 2.475, 2.390, 1.31(40) 1.25(18)
13a″214a″215a″0 2.465; 2.644
tetrahedral-NbSi3 (Cs)
2
A′ 27a′228a′129a′0 2.422, 2.353, 0.00(00) 0.00(00)
13a″214a″215a″0 2.455, 2.643
2
A″ 27a′228a′229a′0 2.337, 2.395, −0.00(42) 0.00(04)
13a″214a″115a″0 2.576, 2.407
4
A″ 27a′228a′129a′1 2.463, 2.463, 1.23 1.21
13a″214a″115a″0 2.449, 2.448
tetrahedral-NbSi3+ (Cs)
3
A″ 27a′228a′129a′0 2.394, 2.394, 0.00 0.00
13a″214a″115a″0 2.501, 2.501
1
A′ 27a′228a′229a′0 2.319, 2.453, 0.49 0.60
13a″214a″015a″0 2.604, 2.316
3
A′ 27a′128a′129a′0 2.432, 2.481, 0.51 0.76
13a″214a″215a″0 3.041, 2.349
Figure 5. Relevant active orbitals and occupation numbers of the 3A2 a
ground state of the NbSi2− cluster as obtained from the CASSCF The bond distances are obtained from the BP86 functional
calculations. calculations. bSingle-point energy calculations with an active space
of (18e, 17e, 16e; 15o) for CASPT2 and of (18e, 17e, 16e; 18o) for
DMRG-CASPT2 based on the geometries optimized with the BP86
Table 4. Adiabatic and Vertical Detachment Energies of functional.
NbSi2− and Adiabatic and Vertical Ionization Energies (AIEs
and VIEs) NbSi2 Clusters Obtained from the DMRG-
CASPT2 Calculations (or 3A2 state in C3v symmetry) as the cationic ground state,
whereas the B3LYP functional favors the 3A1 state in C3v
cluster transition orbital ADE (AIE) (eV) VDE (VIE) (eV) symmetry.10
NbSi2−/0 3
A2 → 4B1 10b2 1.47 1.64 Table 6 displays the electron detachment energies of the
3
A2 → 2A2 17a1 1.83 anionic and neutral ground states. Transitions from the anionic
1
3
A2 → 2A1 3a2 1.88 A′ ground state to the neutral 12A′, 12A″, 22A′, 22A″, 32A′, and
3
A2 → 4B2 6b1 2.69 42A′ states are one-electron detachment processes in which an
NbSi20/+ 4
B 1 → 3B 1 17a1 6.93 6.95 electron is detached from the 28a′, 14a″, 26a′, 13a″, 27a′, and
25a′ orbital, respectively. The ADEs of the transitions to the
neutral 12A′ and 12A″ ground states are both 2.11 eV at the
the doubly degenerate 2E state in the C3v point group. The 2A′ DMRG-CASPT2 level. The VDEs of these transitions are 2.22,
state has Nb−Si bonds of 2.422 and 2.353 Å and Si−Si bonds of 2.21, 3.09, 3.10, 3.19, and 3.96 eV.
2.455 and 2.643 Å. In the 2A′ state, the orders of Nb−Si bonds The computed electron detachment energies are employed to
(r1, r2) are 2.21 and 2.48, while those of Si−Si bonds (r3, r4) are give assignments for the recorded photoelectron spectrum of the
1.15 and 0.88. In the cationic cluster, 3A″ is the ground state with NbSi3− cluster.11 The 266 nm photoelectron spectrum in Figure
Nb−Si bond length of 2.394 Å and Si−Si bond length of 2.501 7 shows three bands centered at 2.28, 3.17, and 3.97 eV, and the
Å. The orders of Nb−Si bonds (r1, r2) in the triplet ground state ADE of the first band is measured to be 1.94 eV. The
are 2.16, and those of Si−Si bonds (r3, r4) are 1.04. The 3A″ experimental error limits of ADE and VDEs are reported to be as
ground state shows a precise C3v structure and therefore much as ±0.08 eV. The first band at 2.28 eV is explained by the
corresponds to the 3A2 state in the C3v point group. The neutral transitions from the anionic 1A′ ground state to the neutral 12A′
2
A′ ground state can be transformed into the anionic 1A′ and and 12A″ states with VDEs of 2.22 and 2.21 eV. The calculated
cationic 3A″ ground states by adding and removing one electron ADE of 2.11 eV of the transition to the 12A′ state is slightly larger
from the 28a′ and 14a″ orbitals, respectively. These orbitals are than the experimental value of 1.94 eV. This discrepancy in ADE
important bonding orbitals between the 4d orbital of Nb and the can be reduced since the uncertainties in the experimental
3p orbital of the Si3 moiety, as shown in Figure 6. Overall, our detachment energies are determined to be ±0.08 eV. The
calculations predict 1A′, 2A′, and 3A″ as the ground states of multidimensional Franck−Condon factor simulations for the
NbSi3−/0/+ clusters. On the anionic and neutral ground states, transitions to 12A′ and 12A″ states in Figure 3d,e reveal extensive
our results agree with the B3LYP functional calculations.10,11 vibrational progressions due to the strong structural relaxation.
However, the DMRG-CASPT2 method computes the 3A″ state The frequency of the most intense progression of the transition
4092 https://doi.org/10.1021/acs.jpca.3c01230
J. Phys. Chem. A 2023, 127, 4086−4095
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Figure 7. Photoelectron spectrum of NbSi3− as recorded with photon

energy of 266 nm.11 The blue and red lines represent the calculated
ADEs and VDEs, respectively. Reproduced with permission from ref 11.
Copyright 2016 Royal Society of Chemistry.

4. CONCLUSION
The electronic states of NbSin−/0/+ (n = 1−3) clusters are
explored with a combination of DFT, CASPT2, and DMRG-
CASPT2 methods. Table 7 summarizes the electron detachment

Table 7. Adiabatic and Vertical Detachment Energies (ADEs

and VDEs) of the Anionic Clusters and the Adiabatic and
Vertical Ionization Energies (AIEs and VIEs) of the Neutral
Clusters As Computed with the DMRG-CASPT2 Method
ADE VDE AIE VIE
cluster state (eV) (eV) cluster state (eV) (eV)
NbSi− 3
Δ 1.59 1.61 NbSi 4
Π 6.77 6.77
NbSi2− 3
A2 1.47 1.64 NbSi2 4
B1 6.93 6.95
Figure 6. Relevant active orbitals and occupation numbers of the 1A′ NbSi3− 1
A′ 2.11 2.22 NbSi3 2
A′ 6.90 7.07
ground state of the tetrahedral NbSi3− isomer as obtained from the
CASSCF calculations.
energies of the anionic clusters and ionization energies of the
to the 12A′ state is 203 cm−1, while that of the transition to the neutral clusters, as obtained with the DMRG-CASPT2 method.
12A″ state is 341 cm−1. The extensive vibrational progressions of The detachment energies of the anionic clusters display minimal
the transitions to 12A′ and 12A″ states result in a wide band at changes during the transition from the 3Δ state of NbSi− to the
2.28 eV. The second band at 3.17 eV is interpreted by the 3
A2 state of NbSi2− but experience a significant increase when
transitions to 22A′, 22A″, and 32A′ states with the calculated moving toward the 1A′ state of NbSi3−. The ionization energies
VDEs of 3.09, 3.10, and 3.19 eV. The third band at 3.97 eV is of the neutral clusters show a slight increase from the 4Π state of
elucidated by the transition to the 42A′ state with an estimated NbSi to the 4B1 state of NbSi2 and the 2A′ state of NbSi3. The
VDE of 3.96 eV. Our findings are consistent with the previous calculated electron detachment energies of the removals of one
B3LYP calculations in which the first ADE and VDE of the electron from various orbitals of the anionic ground states are
anionic cluster are evaluated to be 2.22 and 2.32 eV.11 used to analyze the photoelectron spectra of NbSi− and NbSi3−
Otherwise, a transition from the 2A′ to 3A″ state within clusters. The X band at 1.83 eV in the photoelectron spectrum of
NbSi30/+ clusters has AIE and VIE of 6.90 and 7.07 eV as NbSi− is attributed to the transitions from the anionic 3Δ ground
computed with the DMRG-CASPT2 method. state to the neutral 4Π, 4Φ, and 4Δ states, while the A band at

Table 6. ADEs and VDEs of NbSi3− and AIEs and VIEs of NbSi3 Cluster As Obtained from the CASPT2 and DMRG-CASPT2
Calculations
ADE (AIE) (eV) VDE (VIE) (eV)
transition orbital CASPT2 DMRG-CASPT2 expt.a CASPT2 DMRG-CASPT2 expt.a
tetrahedral-NbSi3−/0
1
A′ → 12A′ 28a′ 2.21 2.11 1.94 2.33 2.22 2.28
1
A′ → 12A″ 14a″ 2.21 2.11 1.94 2.32 2.21 2.28
1
A′ → 22A′ 26a′ 3.11 3.09 3.17
1
A′ → 22A″ 13a″ 3.20 3.10 3.17
1
A′ → 32A′ 27a′ 3.26 3.19 3.17
1
A′ → 42A′ 25a′ 4.07 3.96 3.97
tetrahedral-NbSi30/+
2
A′ → 3A″ 14a″ 7.10 6.90 7.16 7.07

a
Ref 11. The experimental error limits are within ±0.08 eV.

4093 https://doi.org/10.1021/acs.jpca.3c01230
J. Phys. Chem. A 2023, 127, 4086−4095
The Journal of Physical Chemistry A
2.06 eV is assigned to the transition to the neutral 2Δ, 2Σ+, and
2
Φ states. Electron detachments from the anionic 1A′ ground
state are used to analyze the photoelectron spectrum of the
NbSi3− cluster. The first band at 2.28 eV is explained by the
transitions to 12A′ and 12A″ states, the second band at 3.17 eV is
interpreted by the transitions to 22A′, 22A″, and 32A′ states, and
the third band at 3.97 eV is elucidated by the transitions to the
42A′ state. The Franck−Condon factor simulations reveal
intense vibrational progressions for the transition from the
anionic 1A′ ground state to the neutral 2A′ and 2A″ states within
NbSi3−/0 clusters because of the substantial structural relaxation.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpca.3c01230.
Cartesian coordinates of the low-lying states of NbSin−/0/+
(n = 2−3) clusters (Table S1); the absolute energies (AE)
in hartree of the electronic states of NbSi−/0/+ clusters
(Table S2); the vibrational frequencies, relative energies
(REs), and absolute energies (AEs) of the electronic
states of NbSi2−/0/+ clusters (Table S3); and the
vibrational frequencies, relative energies (REs), and
absolute energies (AEs) of the electronic states of
NbSi3−/0/+ clusters (Table S4) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Van Tan Tran − Theoretical and Physical Chemistry Division,
Dong Thap University, Cao Lanh City, Dong Thap 871000,
Vietnam; orcid.org/0000-0001-7878-1327;
Email: tvtan@dthu.edu.vn
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpca.3c01230
Notes
The author declares no competing financial interest.
■ ACKNOWLEDGMENTS
This research is supported by the project B2021.SPD.04.
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