Quantum chemical study of NbSi5−/0 clusters: structures and electron detachment energies
Nội dung chính của bài viết
Tóm tắt
The structures and properties of the NbSi5−/0 cluster have been studied using density functional theory (DFT) and the CASPT2 method. The ground states of the negatively charged and neutral clusters were established as the 1A1 and 2B1 states of a tetragonal bipyramidal isomer with C4v symmetry. The adiabatic and vertical detachment energies (ADE and VDEs) of the transition from the anionic ground state to the neutral ground state were found to be 2.72 and 2.74 eV, respectively. A vibrational progression with three peaks at a frequency of 212 cm−1 was observed for this transition in the Franck-Condon factor simulation. Furthermore, the VDEs of the transitions to the excited 2B1, 12A1, 12E, 22E, and 22A1 states were computed as 3.10, 3.32, 3.77, and 4.67 eV, respectively. The recorded photoelectron spectrum of the NbSi5− cluster was elucidated by the transitions to the 2B1, 12A1, 12E, and 22E states.
Từ khóa
Electron detachment energy, electronic state, Franck-Condon factor, geometrical structure, relative energy
Chi tiết bài viết
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
Tài liệu tham khảo
Borrelli, R., & Peluso, A. (2003). Dynamics of Radiationless Transitions in Large Molecular Systems: A Franck–Condon-Based Method Accounting for Displacements and Rotations of all the Normal Coordinates. The Journal of Chemical Physics, 119(16), 8437–8448. https://doi.org/10.1063/1.1609979
Borrelli, R., & Peluso, A. (2008). The Electron Photodetachment Spectrum of c-C4F8−: A Test Case for the Computation of Franck-Condon Factors of Highly Flexible Molecules. The Journal of Chemical Physics, 128(4), 044303. https://doi.org/10.1063/1.2819061
Fdez. Galván, I., Vacher, M., Alavi, A., Angeli, C., Aquilante, F., Autschbach, J., Bao, J. J., Bokarev, S. I., Bogdanov, N. A., Carlson, R. K., Chibotaru, L. F., Creutzberg, J., Dattani, N., Delcey, M. G., Dong, S. S., Dreuw, A., Freitag, L., Frutos, L. M., Gagliardi, L., … Lindh, R. (2019). OpenMolcas: From Source Code to Insight. Journal of Chemical Theory and Computation, 15(11), 5925–5964. https://doi.org/10.1021/acs.jctc.9b00532
Gunaratne, K. D. D., Berkdemir, C., Harmon, C. L., & Castleman, A. W. (2013). Probing the Valence Orbitals of Transition Metal–Silicon Diatomic Anions: ZrSi, NbSi, MoSi, PdSi and WSi. Physical Chemistry Chemical Physics, 15(16), 6068–6079. https://doi.org/10.1039/C3CP44473B
Hamrick, Y. M., & Weltner, W. (1991). Quenching of Angular Momentum in the Ground States of VC, NbC, VSi, and NbSi Molecules. The Journal of Chemical Physics, 94(5), 3371–3380. https://doi.org/10.1063/1.460688
Koyasu, K., Atobe, J., Akutsu, M., Mitsui, M., & Nakajima, A. (2007). Electronic and Geometric Stabilities of Clusters with Transition Metal Encapsulated by Silicon. The Journal of Physical Chemistry A, 111(1), 42–49. https://doi.org/10.1021/jp066757f
Koyasu, K., Atobe, J., Furuse, S., & Nakajima, A. (2008). Anion Photoelectron Spectroscopy of Transition Metal- and Lanthanide Metal-Silicon Clusters: MSin− (n = 6–20). The Journal of Chemical Physics, 129(21), 214301. https://doi.org/10.1063/1.3023080
Lu, S.-J., Cao, G.-J., Xu, X.-L., Xu, H.-G., & Zheng, W.-J. (2016). The Structural and Electronic Properties of NbSin−/0 (n = 3–12) Clusters: Anion Photoelectron Spectroscopy and Ab Initio Calculations. Nanoscale, 8(47), 19769–19778. https://doi.org/10.1039/C6NR07480D
Nguyen, M. T., Tran, Q. T., & Tran, V. T. (2017). A CASSCF/CASPT2 Investigation on Electron Detachments from ScSin− (n = 4–6) Clusters. Journal of Molecular Modeling, 23(10), 282. https://doi.org/10.1007/s00894-017-3461-2
Nguyen, M. T., Tran, Q. T., & Tran, V. T. (2019). The Ground and Excited Low-Lying States of VSi20/−/+ Clusters from CASSCF/CASPT2 Calculations. Chemical Physics Letters, 721, 111–116. https://doi.org/10.1016/j.cplett.2019.02.043
Oakley, M. S., Gagliardi, L., & Truhlar, D. G. (2021). Multiconfiguration Pair-Density Functional Theory for Transition Metal Silicide Bond Dissociation Energies, Bond Lengths, and State Orderings. Molecules, 26(10), 2881. https://doi.org/10.3390/molecules26102881
Pham, L. N., & Nguyen, M. T. (2016). Electronic Structure of Neutral and Anionic Scandium Disilicon ScSi2–/0 Clusters and the Related Anion Photoelectron Spectrum. The Journal of Physical Chemistry A, 120(47), 9401–9410. https://doi.org/10.1021/acs.jpca.6b09067
Pham, L. N., & Nguyen, M. T. (2017). Insights into Geometric and Electronic Structures of VGe3–/0 Clusters from Anion Photoelectron Spectrum Assignment. The Journal of Physical Chemistry A, 121(37), 6949–6956. https://doi.org/10.1021/acs.jpca.7b07459
Roos, B. O., Lindh, R., Malmqvist, P.-Å., Veryazov, V., & Widmark, P.-O. (2004). Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set. The Journal of Physical Chemistry A, 108(15), 2851–2858. https://doi.org/10.1021/jp031064+
Roos, B. O., Lindh, R., Malmqvist, P.-Å., Veryazov, V., & Widmark, P.-O. (2005). New Relativistic ANO Basis Sets for Transition Metal Atoms. The Journal of Physical Chemistry A, 109(29), 6575–6579. https://doi.org/10.1021/jp0581126
Sevy, A., Sorensen, J. J., Persinger, T. D., Franchina, J. A., Johnson, E. L., & Morse, M. D. (2017). Bond Dissociation Energies of TiSi, ZrSi, HfSi, VSi, NbSi, and TaSi. The Journal of Chemical Physics, 147(8), 084301. https://doi.org/10.1063/1.4986213
Thao, N. M., Hanh, N. T. H., Tuan, T. T., Tri, T. Q., & Van Tan, T. (2018). An Investigation on the Electronic Structures of Diatomic VSi0/–/+ Clusters by CASSCF/CASPT2 Method. Vietnam Journal of Chemistry, 56(4), 483–487. https://doi.org/10.1002/vjch.201800034
Tran, Q. T., & Tran, V. T. (2016). Quantum Chemical Study of the Geometrical and Electronic Structures of ScSi3−/0 Clusters and Assignment of the Anion Photoelectron Spectra. The Journal of Chemical Physics, 144(21), 214305. https://doi.org/10.1063/1.4953082
Tran, V. T. (2023). Electron Detachments of NbSin–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations. The Journal of Physical Chemistry A, 127(18), 4086–4095. https://doi.org/10.1021/acs.jpca.3c01230
Tran, V. T., & Hendrickx, M. F. A. (2014). Molecular and Electronic Structures of the NbC2−/0 Clusters through the Assignment of the Anion Photoelectron Spectra by Quantum Chemical Calculations. Chemical Physics Letters, 609, 98–103. https://doi.org/10.1016/j.cplett.2014.06.046
Tran, V. T., Nguyen, M. T., & Tran, Q. T. (2017). Computational Investigation of the Geometrical and Electronic Structures of VGen–/0 (n = 1–4) Clusters by Density Functional Theory and Multiconfigurational CASSCF/CASPT2 Method. The Journal of Physical Chemistry A, 121(40), 7787–7796. https://doi.org/10.1021/acs.jpca.7b08351
Tran, V. T., & Tran, Q. T. (2016). Quantum Chemical Study of the Low-Lying Electronic States of VSi3–/0 Clusters and Interpretation of the Anion Photoelectron Spectrum. The Journal of Physical Chemistry A, 120(29), 5950–5957. https://doi.org/10.1021/acs.jpca.6b05653
Tran, V. T., & Tran, Q. T. (2018). Spin State Energetics of VGen−/0 (n = 5–7) Clusters and New Assignments of the Anion Photoelectron Spectra. Journal of Computational Chemistry, 39(25), 2103–2109. https://doi.org/10.1002/jcc.25527
Tran, V. T., Tran, Q. T., & Hendrickx, M. F. A. (2019). Ground and Low-Lying Excited States of NbC3–/0 Clusters: Assignment of the Anion Photoelectron Spectra from Multiconfigurational Calculations. The Journal of Physical Chemistry A, 123(38), 8265–8273. https://doi.org/10.1021/acs.jpca.9b07583
Tran, V. T., Tran, X. M. T., Nguyen, M. T., Nguyen, H. T., & Tran, Q. T. (2017). A New Interpretation of the Photoelectron Spectrum of VSi4− Cluster by Density Functional Theory and Multiconfigurational CASSCF/CASPT2 Calculations. Chemical Physics Letters, 690, 140–146. https://doi.org/10.1016/j.cplett.2017.10.049
Valiev, M., Bylaska, E. J., Govind, N., Kowalski, K., Straatsma, T. P., Van Dam, H. J. J., Wang, D., Nieplocha, J., Apra, E., Windus, T. L., & de Jong, W. A. (2010). NWChem: A Comprehensive and Scalable Open-Source Solution for Large Scale Molecular Simulations. Computer Physics Communications, 181(9), 1477–1489. https://doi.org/10.1016/j.cpc.2010.04.018
Wu, Z. J., & Su, Z. M. (2006). Electronic Structures and Chemical Bonding in Transition Metal Monosilicides MSi (M = 3d, 4d, 5d Elements). Journal of Chemical Physics, 124(18), 184306. https://doi.org/10.1063/1.2196040
Xia, X. X., Hermann, A., Kuang, X. Y., Jin, Y. Y., Lu, C., & Xing, X. D. (2016). Study of the Structural and Electronic Properties of Neutral and Charged Niobium-Doped Silicon Clusters: Niobium Encapsulated in Silicon Cages. The Journal of Physical Chemistry C, 120(1), 677–684. https://doi.org/10.1021/acs.jpcc.5b09453
Borrelli, R., & Peluso, A. (2008). The Electron Photodetachment Spectrum of c-C4F8−: A Test Case for the Computation of Franck-Condon Factors of Highly Flexible Molecules. The Journal of Chemical Physics, 128(4), 044303. https://doi.org/10.1063/1.2819061
Fdez. Galván, I., Vacher, M., Alavi, A., Angeli, C., Aquilante, F., Autschbach, J., Bao, J. J., Bokarev, S. I., Bogdanov, N. A., Carlson, R. K., Chibotaru, L. F., Creutzberg, J., Dattani, N., Delcey, M. G., Dong, S. S., Dreuw, A., Freitag, L., Frutos, L. M., Gagliardi, L., … Lindh, R. (2019). OpenMolcas: From Source Code to Insight. Journal of Chemical Theory and Computation, 15(11), 5925–5964. https://doi.org/10.1021/acs.jctc.9b00532
Gunaratne, K. D. D., Berkdemir, C., Harmon, C. L., & Castleman, A. W. (2013). Probing the Valence Orbitals of Transition Metal–Silicon Diatomic Anions: ZrSi, NbSi, MoSi, PdSi and WSi. Physical Chemistry Chemical Physics, 15(16), 6068–6079. https://doi.org/10.1039/C3CP44473B
Hamrick, Y. M., & Weltner, W. (1991). Quenching of Angular Momentum in the Ground States of VC, NbC, VSi, and NbSi Molecules. The Journal of Chemical Physics, 94(5), 3371–3380. https://doi.org/10.1063/1.460688
Koyasu, K., Atobe, J., Akutsu, M., Mitsui, M., & Nakajima, A. (2007). Electronic and Geometric Stabilities of Clusters with Transition Metal Encapsulated by Silicon. The Journal of Physical Chemistry A, 111(1), 42–49. https://doi.org/10.1021/jp066757f
Koyasu, K., Atobe, J., Furuse, S., & Nakajima, A. (2008). Anion Photoelectron Spectroscopy of Transition Metal- and Lanthanide Metal-Silicon Clusters: MSin− (n = 6–20). The Journal of Chemical Physics, 129(21), 214301. https://doi.org/10.1063/1.3023080
Lu, S.-J., Cao, G.-J., Xu, X.-L., Xu, H.-G., & Zheng, W.-J. (2016). The Structural and Electronic Properties of NbSin−/0 (n = 3–12) Clusters: Anion Photoelectron Spectroscopy and Ab Initio Calculations. Nanoscale, 8(47), 19769–19778. https://doi.org/10.1039/C6NR07480D
Nguyen, M. T., Tran, Q. T., & Tran, V. T. (2017). A CASSCF/CASPT2 Investigation on Electron Detachments from ScSin− (n = 4–6) Clusters. Journal of Molecular Modeling, 23(10), 282. https://doi.org/10.1007/s00894-017-3461-2
Nguyen, M. T., Tran, Q. T., & Tran, V. T. (2019). The Ground and Excited Low-Lying States of VSi20/−/+ Clusters from CASSCF/CASPT2 Calculations. Chemical Physics Letters, 721, 111–116. https://doi.org/10.1016/j.cplett.2019.02.043
Oakley, M. S., Gagliardi, L., & Truhlar, D. G. (2021). Multiconfiguration Pair-Density Functional Theory for Transition Metal Silicide Bond Dissociation Energies, Bond Lengths, and State Orderings. Molecules, 26(10), 2881. https://doi.org/10.3390/molecules26102881
Pham, L. N., & Nguyen, M. T. (2016). Electronic Structure of Neutral and Anionic Scandium Disilicon ScSi2–/0 Clusters and the Related Anion Photoelectron Spectrum. The Journal of Physical Chemistry A, 120(47), 9401–9410. https://doi.org/10.1021/acs.jpca.6b09067
Pham, L. N., & Nguyen, M. T. (2017). Insights into Geometric and Electronic Structures of VGe3–/0 Clusters from Anion Photoelectron Spectrum Assignment. The Journal of Physical Chemistry A, 121(37), 6949–6956. https://doi.org/10.1021/acs.jpca.7b07459
Roos, B. O., Lindh, R., Malmqvist, P.-Å., Veryazov, V., & Widmark, P.-O. (2004). Main Group Atoms and Dimers Studied with a New Relativistic ANO Basis Set. The Journal of Physical Chemistry A, 108(15), 2851–2858. https://doi.org/10.1021/jp031064+
Roos, B. O., Lindh, R., Malmqvist, P.-Å., Veryazov, V., & Widmark, P.-O. (2005). New Relativistic ANO Basis Sets for Transition Metal Atoms. The Journal of Physical Chemistry A, 109(29), 6575–6579. https://doi.org/10.1021/jp0581126
Sevy, A., Sorensen, J. J., Persinger, T. D., Franchina, J. A., Johnson, E. L., & Morse, M. D. (2017). Bond Dissociation Energies of TiSi, ZrSi, HfSi, VSi, NbSi, and TaSi. The Journal of Chemical Physics, 147(8), 084301. https://doi.org/10.1063/1.4986213
Thao, N. M., Hanh, N. T. H., Tuan, T. T., Tri, T. Q., & Van Tan, T. (2018). An Investigation on the Electronic Structures of Diatomic VSi0/–/+ Clusters by CASSCF/CASPT2 Method. Vietnam Journal of Chemistry, 56(4), 483–487. https://doi.org/10.1002/vjch.201800034
Tran, Q. T., & Tran, V. T. (2016). Quantum Chemical Study of the Geometrical and Electronic Structures of ScSi3−/0 Clusters and Assignment of the Anion Photoelectron Spectra. The Journal of Chemical Physics, 144(21), 214305. https://doi.org/10.1063/1.4953082
Tran, V. T. (2023). Electron Detachments of NbSin–/0 (n = 1–3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations. The Journal of Physical Chemistry A, 127(18), 4086–4095. https://doi.org/10.1021/acs.jpca.3c01230
Tran, V. T., & Hendrickx, M. F. A. (2014). Molecular and Electronic Structures of the NbC2−/0 Clusters through the Assignment of the Anion Photoelectron Spectra by Quantum Chemical Calculations. Chemical Physics Letters, 609, 98–103. https://doi.org/10.1016/j.cplett.2014.06.046
Tran, V. T., Nguyen, M. T., & Tran, Q. T. (2017). Computational Investigation of the Geometrical and Electronic Structures of VGen–/0 (n = 1–4) Clusters by Density Functional Theory and Multiconfigurational CASSCF/CASPT2 Method. The Journal of Physical Chemistry A, 121(40), 7787–7796. https://doi.org/10.1021/acs.jpca.7b08351
Tran, V. T., & Tran, Q. T. (2016). Quantum Chemical Study of the Low-Lying Electronic States of VSi3–/0 Clusters and Interpretation of the Anion Photoelectron Spectrum. The Journal of Physical Chemistry A, 120(29), 5950–5957. https://doi.org/10.1021/acs.jpca.6b05653
Tran, V. T., & Tran, Q. T. (2018). Spin State Energetics of VGen−/0 (n = 5–7) Clusters and New Assignments of the Anion Photoelectron Spectra. Journal of Computational Chemistry, 39(25), 2103–2109. https://doi.org/10.1002/jcc.25527
Tran, V. T., Tran, Q. T., & Hendrickx, M. F. A. (2019). Ground and Low-Lying Excited States of NbC3–/0 Clusters: Assignment of the Anion Photoelectron Spectra from Multiconfigurational Calculations. The Journal of Physical Chemistry A, 123(38), 8265–8273. https://doi.org/10.1021/acs.jpca.9b07583
Tran, V. T., Tran, X. M. T., Nguyen, M. T., Nguyen, H. T., & Tran, Q. T. (2017). A New Interpretation of the Photoelectron Spectrum of VSi4− Cluster by Density Functional Theory and Multiconfigurational CASSCF/CASPT2 Calculations. Chemical Physics Letters, 690, 140–146. https://doi.org/10.1016/j.cplett.2017.10.049
Valiev, M., Bylaska, E. J., Govind, N., Kowalski, K., Straatsma, T. P., Van Dam, H. J. J., Wang, D., Nieplocha, J., Apra, E., Windus, T. L., & de Jong, W. A. (2010). NWChem: A Comprehensive and Scalable Open-Source Solution for Large Scale Molecular Simulations. Computer Physics Communications, 181(9), 1477–1489. https://doi.org/10.1016/j.cpc.2010.04.018
Wu, Z. J., & Su, Z. M. (2006). Electronic Structures and Chemical Bonding in Transition Metal Monosilicides MSi (M = 3d, 4d, 5d Elements). Journal of Chemical Physics, 124(18), 184306. https://doi.org/10.1063/1.2196040
Xia, X. X., Hermann, A., Kuang, X. Y., Jin, Y. Y., Lu, C., & Xing, X. D. (2016). Study of the Structural and Electronic Properties of Neutral and Charged Niobium-Doped Silicon Clusters: Niobium Encapsulated in Silicon Cages. The Journal of Physical Chemistry C, 120(1), 677–684. https://doi.org/10.1021/acs.jpcc.5b09453
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