Multistate Density Function Theory and the Construction of Diabatic and Adiabatic Potential Energy Surfaces†

doi:10.7503/cjcu20150629

Abstract

Abstract:

A multistate density function theory(MSDFT) based on valence bond theory was introduced. As an application, the MSDFT method was illustrated by the bond dissociation of H₂ and the proton transfer between HNO₃ and a water molecule. In the dissociation of H₂, the MSDFT method yields a correct behavior as the two H atoms stretch to infinity, and gives a potential well in accord with second-order perturbation using complete active space(CASPT2). For the proton transfer process of HNO₃, MSDFT can be used to yield both diabatic and adiabatic potential energy curves as a function of the proton transfer reaction coordinate. For the reaction barrier height, the inclusion of an ionic state in a three-state model can significantly improve the accuracy in barrier height in comparison with the high-level results.

Key words: Multistate density function theory, Diabatic state, Non-adiabatic coupling, Potential energy surface

CLC Number:

O641

TrendMD:

QU Zexing, GAO Jiali. Multistate Density Function Theory and the Construction of Diabatic and Adiabatic Potential Energy Surfaces^†[J]. Chem. J. Chinese Universities, 2015, 36(11): 2236.

Figures/Tables 3

Fig.1 Computed adiabatic ground state energy profile for the dissociation of H2 using CASPT2(2,2), CASSCF(2,2), HF, B3LYP and MSDFT methods with the aug-cc-pvtz basis set

Fig.2 Computed adiabatic ground state energy profile(in green) for hydrogen transfer between HNO3 and H2O and diabatic energy curves of reaction state(H11 in black) and product state(H22 in red) as well as the coupling energy(V12 in blue) computed using MSDFT method

Fig.3 Adiabatic ground state potential energy curves calculated using the hybrid B3LYP method, the MSDFT(2) method with two states, and MSDFT(3) method with three states

References 31

[1]	Subotnik J. E., Yeganeh S., Cave R. J., Ratner M. A., J. Chem. Phys., 2008, 129, 244101
[2]	Song L., Gao J., J. Phys. Chem. A, 2008, 112, 12925—12935
[3]	Mo Y., J. Chem. Phys., 2007, 126, 224104
[4]	Hoyer C. E., Xu X., Ma D., Gagliardi L., Truhlar D. G., J. Chem. Phys., 2014, 141, 114104
[5]	Shearer J., Schmitt J. C., Clewett H. S., J. Phys. Chem. B, 2015, 119, 5453—5461
[6]	Subotnic J. E., Alguire E. C., Ou Q., Landry B. R., Fatehi S., Acc. Chem. Res., 2015, 48, 1340—1350
[7]	Wu Q., vanVoorhis T., J. Chem. Phys., 2006, 125, 164105
[8]	Ye S., Geng C. Y., Shaik S., Neese F., Phys. Chem. Chem. Phys., 2013, 15, 8017—8030
[9]	Mo Y., Song L., Lin Y., Liu M., Cao Z., Wu W., J. Chem. Theory Comput., 2012, 8, 800—805
[10]	Chen H., Song J., Lai W., Wu W., Shaik S., J. Chem. Theory Comput., 2010, 6, 940—953
[11]	Steinmann S. N., Corminboeuf C., Wu W., Mo Y., J. Phys. Chem. A, 2011, 115, 5467—5477
[12]	Song L., Mo Y., Zhang Q., Wu W., J. Comput. Chem., 2005, 26, 514—521
[13]	Chen Z., Chen X., Wu W., J. Chem. Phys., 2013, 138, 164120
[14]	Chang X., Su P., Wu W., Chem. Phys. Lett., 2014, 610, 246—250
[15]	Wu W., Su P. F., Shaik S., Hiberty P. C., Chem. Rev., 2011, 111, 7557—7593
[16]	Song L., Mo Y., Gao J., J. Chem. Theory Comput., 2009, 5, 174—185
[17]	Gao J., Cembran A., Mo Y., J. Chem. Theory Comput., 2010, 6, 2402—2410
[18]	Song L., Gao J., J. Phys. Chem. A, 2008, 112, 12925—12935
[19]	Mo Y., Gao J., J. Phys. Chem. A, 2000, 104, 3012—3020
[20]	Cembran A., Provorse M. R., Wang C., Wei W., Gao J., J. Chem. Theory Comput., 2012, 8, 4347—4358
[21]	Cembarn A., Song L., Mo Y., Gao J., J. Chem. Theory Comput., 2009, 5, 2702—2716
[22]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., et al., Gaussian 09, Revision D.01, Gaussian Inc., Wallingford CT, 2010
[23]	Werner H.J., Knowles P. J., Lindh R., Manby F. R., Schutz M., Celani P., Korona T., Rauhut G., Amos R. D., Bernhardsson A., et al., MOLPRO, Version 2010.1., A Package of ab initio Programs,
[24]	Schmidt M. W., Baldrdge K.K., Boatz J. A., Elbert S. T., Gordon M. S., Jensen J. H., Koseki S., Matsunaga N., Nguyen K. A., et al., J. Comput. Chem., 1993, 14, 1347—1363
[25]	Werner H. J., Mol. Phys., 1996, 89, 645—661
[26]	McCurdy P. R., Hess W. P. Xantheas S. S., J. Phys. Chem. A, 2002, 106, 7628—7653
[27]	Sedo G., Doran J. L., Leopold K. R., J. Phys. Chem. A, 2009, 113, 11301—11310
[28]	Bianco R., Wang S., Hynes J. T., J. Phys. Chem. A, 2007, 111, 11033—11042
[29]	Leopold K. R., Annu. Rev. Phys. Chem., 2011, 62, 327—349
[30]	Scott J. R., Wright J. B., J. Phys. Chem. A, 2004, 108, 10578—10585
[31]	D’Auria R., Turco R. P., Houk K. N., J. Phys. Chem. A, 2004, 108, 3756—3765