Curing the Divergence in Time-Dependent Density Functional Quadratic Response Theory

被引：0

作者：

Dar, Davood ^{[1
]}

Roy, Saswata ^{[1
]}

Maitra, Neepa T. ^{[1
]}

机构：

[1] Rutgers State Univ, Dept Phys, Newark, NJ 07102 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2023年 / 14卷 / 13期

基金：

美国国家科学基金会;

关键词：

EXCITED-STATES; DERIVATIVE COUPLINGS; EXCITATION-ENERGIES; NONLINEAR-RESPONSE;

D O I：

10.1021/acs.jpclett.3c001223186J

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The adiabatic approximation in time-dependent density functional theory is known to give an incorrect pole structure in the quadratic response function, leading to unphysical divergences in excited state-to-state transition probabilities and hyperpolarizabilties. We find the form of the exact quadratic response kernel and derive a practical and accurate approximation that cures the divergence. We demonstrate our results on excited state-to-state transition probabilities of a model system and of the LiH molecule.

引用

页码：3186 / 3192

页数：7

共 44 条

[1] Toward reliable density functional methods without adjustable parameters: The PBE0 model [J].

Adamo, C ;

Barone, V .

JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) :6158-6170

[2] The Dalton quantum chemistry program system [J].

Aidas, Kestutis ;

Angeli, Celestino ;

Bak, Keld L. ;

Bakken, Vebjorn ;

Bast, Radovan ;

Boman, Linus ;

Christiansen, Ove ;

Cimiraglia, Renzo ;

Coriani, Sonia ;

Dahle, Pal ;

Dalskov, Erik K. ;

Ekstrom, Ulf ;

Enevoldsen, Thomas ;

Eriksen, Janus J. ;

Ettenhuber, Patrick ;

Fernandez, Berta ;

Ferrighi, Lara ;

Fliegl, Heike ;

Frediani, Luca ;

Hald, Kasper ;

Halkier, Asger ;

Hattig, Christof ;

Heiberg, Hanne ;

Helgaker, Trygve ;

Hennum, Alf Christian ;

Hettema, Hinne ;

Hjertenaes, Eirik ;

Host, Stinne ;

Hoyvik, Ida-Marie ;

Iozzi, Maria Francesca ;

Jansik, Branislav ;

Jensen, Hans Jorgen Aa. ;

Jonsson, Dan ;

Jorgensen, Poul ;

Kauczor, Joanna ;

Kirpekar, Sheela ;

Kjrgaard, Thomas ;

Klopper, Wim ;

Knecht, Stefan ;

Kobayashi, Rika ;

Koch, Henrik ;

Kongsted, Jacob ;

Krapp, Andreas ;

Kristensen, Kasper ;

Ligabue, Andrea ;

Lutnaes, Ola B. ;

Melo, Juan I. ;

Mikkelsen, Kurt V. ;

Myhre, Rolf H. ;

Neiss, Christian .

WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE, 2014, 4 (03) :269-284

[3] Calculating Derivative Couplings between Time-Dependent Hartree-Fock Excited States with Pseudo-Wavefunctions [J].

Alguire, Ethan C. ;

Ou, Qi ;

Subotnik, Joseph E. .

JOURNAL OF PHYSICAL CHEMISTRY B, 2015, 119 (24) :7140-7149

[4] Excitations in time-dependent density-functional theory [J].

Appel, H ;

Gross, EKU ;

Burke, K .

PHYSICAL REVIEW LETTERS, 2003, 90 (04) :4

[5] TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations [J].

Balasubramani, Sree Ganesh ;

Chen, Guo P. ;

Coriani, Sonia ;

Diedenhofen, Michael ;

Frank, Marius S. ;

Franzke, Yannick J. ;

Furche, Filipp ;

Grotjahn, Robin ;

Harding, Michael E. ;

Haettig, Christof ;

Hellweg, Arnim ;

Helmich-Paris, Benjamin ;

Holzer, Christof ;

Huniar, Uwe ;

Kaupp, Martin ;

Khah, Alireza Marefat ;

Khani, Sarah Karbalaei ;

Mueller, Thomas ;

Mack, Fabian ;

Nguyen, Brian D. ;

Parker, Shane M. ;

Perlt, Eva ;

Rappoport, Dmitrij ;

Reiter, Kevin ;

Roy, Saswata ;

Rueckert, Matthias ;

Schmitz, Gunnar ;

Sierka, Marek ;

Tapavicza, Enrico ;

Tew, David P. ;

van Wuellen, Christoph ;

Voora, Vamsee K. ;

Weigend, Florian ;

Wodynski, Artur ;

Yu, Jason M. .

JOURNAL OF CHEMICAL PHYSICS, 2020, 152 (18)

[6] A simplified time-dependent density functional theory approach for electronic ultraviolet and circular dichroism spectra of very large molecules [J].

Bannwarth, Christoph ;

Grimme, Stefan .

COMPUTATIONAL AND THEORETICAL CHEMISTRY, 2014, 1040 :45-53

[7]

Carrascal D. J., EUR PHYS J B

[8]

Casida M. E., 1995, RECENT ADV DENSITY F, P155, DOI [10.1142/9789812830586, DOI 10.1142/9789812830586]

[9] Ab Initio Simulation of Optical Limiting: The Case of Metal-Free Phthalocyanine [J].

Cocchi, Caterina ;

Prezzi, Deborah ;

Ruini, Alice ;

Molinari, Elisa ;

Rozzi, Carlo A. .

PHYSICAL REVIEW LETTERS, 2014, 112 (19)

[10] QUADRATIC RESPONSE FUNCTIONS WITHIN THE TIME-DEPENDENT HARTREE-FOCK APPROXIMATION [J].

DALGAARD, E .

PHYSICAL REVIEW A, 1982, 26 (01) :42-52

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