Generalized Breathing Orbital Valence Bond Approach

doi:10.1007/s40242-025-5172-z

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (5): 1100-1105.doi: 10.1007/s40242-025-5172-z

Generalized Breathing Orbital Valence Bond Approach

YING Fuming, ZHOU Chen, WU Wei

State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China

收稿日期:2025-08-15 接受日期:2025-09-08 出版日期:2025-10-01 发布日期:2025-09-26
通讯作者: WU Wei, E-mail: weiwu@xmu.edu.cn E-mail:weiwu@xmu.edu.cn
基金资助:
This work was supported by the Fundamental Research Funds for the Central Universities, China (No. 20720220015) and the National Natural Science Foundation of China (Nos. 22373077, 22303070).

Generalized Breathing Orbital Valence Bond Approach

YING Fuming, ZHOU Chen, WU Wei

State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China

Received:2025-08-15 Accepted:2025-09-08 Online:2025-10-01 Published:2025-09-26
Contact: WU Wei, E-mail: weiwu@xmu.edu.cn E-mail:weiwu@xmu.edu.cn
Supported by:
This work was supported by the Fundamental Research Funds for the Central Universities, China (No. 20720220015) and the National Natural Science Foundation of China (Nos. 22373077, 22303070).

摘要/Abstract

摘要： We present a novel breathing orbital valence bond (BOVB) scheme, termed generalized BOVB (GBOVB), which constructs the wave function as a linear combination of valence bond self-consistent field (VBSCF) and its excited structures without requiring SCF orbital optimization. By applying different truncation levels to the excited configurations, multiple GBOVB variants are developed, offering flexible trade-offs between computational efficiency and accuracy. Benchmark tests reveal that GBOVB4 achieves the highest accuracy at a greater computational cost, while GBOVB4(D) provides the best balance between performance and efficiency. Notably, GBOVB overcomes convergence challenges of conventional BOVB methods when dealing with delocalized orbitals. Despite these advantages, limitations remain: excitations beyond double excitations may be important, and neglecting interactions between doubly excited structures in GBOVB4(D) can reduce accuracy, especially for systems with large active spaces.

关键词: Valence bond theory, Breathing orbital valence bond, Excited valence bond structure

Abstract: We present a novel breathing orbital valence bond (BOVB) scheme, termed generalized BOVB (GBOVB), which constructs the wave function as a linear combination of valence bond self-consistent field (VBSCF) and its excited structures without requiring SCF orbital optimization. By applying different truncation levels to the excited configurations, multiple GBOVB variants are developed, offering flexible trade-offs between computational efficiency and accuracy. Benchmark tests reveal that GBOVB4 achieves the highest accuracy at a greater computational cost, while GBOVB4(D) provides the best balance between performance and efficiency. Notably, GBOVB overcomes convergence challenges of conventional BOVB methods when dealing with delocalized orbitals. Despite these advantages, limitations remain: excitations beyond double excitations may be important, and neglecting interactions between doubly excited structures in GBOVB4(D) can reduce accuracy, especially for systems with large active spaces.

Key words: Valence bond theory, Breathing orbital valence bond, Excited valence bond structure

YING Fuming, ZHOU Chen, WU Wei. Generalized Breathing Orbital Valence Bond Approach[J]. 高等学校化学研究, 2025, 41(5): 1100-1105.

YING Fuming, ZHOU Chen, WU Wei. Generalized Breathing Orbital Valence Bond Approach[J]. Chemical Research in Chinese Universities, 2025, 41(5): 1100-1105.

参考文献

[1] Roos B. O., Taylor P. R., Siegbahn P. E. M., Chem. Phys., 1980, 48, 157.
[2] Siegbahn P. E. M., Heiberg A., Roos B. O., Levy B., Phys. Scr., 1980, 21, 323.
[3] van Lenthe J. H., Balint-Kurti G. G., Chem. Phys. Lett., 1980, 76, 138.
[4] van Lenthe J. H., Balint-Kurti G. G., J. Chem. Phys., 1983, 78, 5699.
[5] Verbeek J., van Lenthe J. H., J. Mol. Struct.: THEOCHEM, 1991, 229, 1157.
[6] Dijkstra F., van Lenthe J. H., Chem. Phys. Lett., 1999, 310, 553.
[7] Dijkstra F., van Lenthe J. H., J. Chem. Phys., 2000, 113, 2100.
[8] Andersson K., Malmqvist P. Å., Roos B.O., J. Chem. Phys., 1992, 96, 1218.
[9] Nakano H., J. Chem. Phys., 1993, 99, 7983.
[10] Siegbahn P. E. M., Almlöf J., Heiberg A., Roos B. O., J. Chem. Phys., 1981, 74, 2384.
[11] Chen Z., Song J., Shaik S., Hiberty P. C., Wu W., J. Phys. Chem. A, 2009, 113, 11560.
[12] Chen X., Chen Z., Wu W., J. Chem. Phys., 2014, 141, 194113.
[13] Wu W., Song L., Cao Z., Zhang Q., Shaik S., J. Phys. Chem. A, 2002, 106, 2721.
[14] Song L., Wu W., Zhang Q., Shaik S., J. Comput. Chem., 2004, 25, 472.
[15] Hiberty P. C., Flament J. P., Noizet E., Chem. Phys. Lett., 1992, 189, 2595.
[16] Hiberty P. C., Humbel S., Archirel P., J. Phys. Chem., 1994, 98, 11697.
[17] Hiberty P. C., Humbel S., Byrman C. P., van Lenthe J. H., J. Chem. Phys., 1994, 101, 5969.
[18] Hiberty P. C., Shaik S., Theor. Chem. Acc., 2002, 108, 255.
[19] Zhang E., Hirao H., J. Phys. Chem. A, 2024, 128, 7167.
[20] Zhang E., Hirao H., Molecules, 2025, 30, 2242.
[21] Mo Y., Danovich D., Shaik S., J. Mol. Model, 2022, 28, 274.
[22] Shearer J., Vasiliauskas D., Lancaster K. M., Chem. Commun., 2022, 59, 98.
[23] Shaik S., Danovich D., Zare R. N., J. Am. Chem. Soc., 2023, 145, 20132.
[24] Su P., Song L., Wu W., Hiberty P. C., Shaik S., J. Comput. Chem., 2007, 28, 185.
[25] Linstrom P. J., Mallard, W. G., NIST Chemistry WebBook, Gaithersburg, MD: National Institute of Standards and Technology, 2011.
[26] Johnson II R. D., NIST Computational Chemistry Comparison and Benchmark Database (Online), http://cccbdb.nist.gov/, 2018.
[27] Leininger M. L., Nielsen I. M. B., Crawfor T. D., Janssen C. L., Chem. Phys. Lett., 2000, 328, 431.
[28] Mallard W. G., Linstrom, P. J., NIST Chemistry WebBook, Gaithersburg, MD: National Institute of Standards and Technology, 1998.

Generalized Breathing Orbital Valence Bond Approach

Generalized Breathing Orbital Valence Bond Approach

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