Analytic energy derivatives for coupled‐cluster methods describing excited states: General formulas and comparison of computational costs

Research output: Article

92 Citations (Scopus)

Abstract

It is possible to derive energy derivatives for nonvariational (e.g., coupled‐cluster) methods invoking the generalized Hellmann–Feynman theorem. In such a procedure, one constructs a functional which, besides the usual wave‐function parameters, contains new ones. One set of stationary conditions will reproduce exactly the original equations of the method, while the others will determine the value of the new parameters. We applied this straightforward procedure to derive analytic energy derivatives for several coupled‐cluster (CC) methods applicable to excited states such as the Hilbert‐space CC method, two‐determinetal (TD) CC method, Fock‐space CC method, and equation‐of‐motion–CC (EOM–CC) method. Finally, we compared the computational requirements for the different methods. © 1995 John Wiley & Sons, Inc.

Original languageEnglish
Pages (from-to)151-163
Number of pages13
JournalInternational Journal of Quantum Chemistry
Volume55
Issue number2
DOIs
Publication statusPublished - 1995

Fingerprint

Excited states
Derivatives
costs
Wave functions
excitation
Costs
theorems
requirements
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

@article{efb5df099b284164911b0bf6575fed50,
title = "Analytic energy derivatives for coupled‐cluster methods describing excited states: General formulas and comparison of computational costs",
abstract = "It is possible to derive energy derivatives for nonvariational (e.g., coupled‐cluster) methods invoking the generalized Hellmann–Feynman theorem. In such a procedure, one constructs a functional which, besides the usual wave‐function parameters, contains new ones. One set of stationary conditions will reproduce exactly the original equations of the method, while the others will determine the value of the new parameters. We applied this straightforward procedure to derive analytic energy derivatives for several coupled‐cluster (CC) methods applicable to excited states such as the Hilbert‐space CC method, two‐determinetal (TD) CC method, Fock‐space CC method, and equation‐of‐motion–CC (EOM–CC) method. Finally, we compared the computational requirements for the different methods. {\circledC} 1995 John Wiley & Sons, Inc.",
author = "P. Szalay",
year = "1995",
doi = "10.1002/qua.560550210",
language = "English",
volume = "55",
pages = "151--163",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",
number = "2",

}

TY - JOUR

T1 - Analytic energy derivatives for coupled‐cluster methods describing excited states

T2 - General formulas and comparison of computational costs

AU - Szalay, P.

PY - 1995

Y1 - 1995

N2 - It is possible to derive energy derivatives for nonvariational (e.g., coupled‐cluster) methods invoking the generalized Hellmann–Feynman theorem. In such a procedure, one constructs a functional which, besides the usual wave‐function parameters, contains new ones. One set of stationary conditions will reproduce exactly the original equations of the method, while the others will determine the value of the new parameters. We applied this straightforward procedure to derive analytic energy derivatives for several coupled‐cluster (CC) methods applicable to excited states such as the Hilbert‐space CC method, two‐determinetal (TD) CC method, Fock‐space CC method, and equation‐of‐motion–CC (EOM–CC) method. Finally, we compared the computational requirements for the different methods. © 1995 John Wiley & Sons, Inc.

AB - It is possible to derive energy derivatives for nonvariational (e.g., coupled‐cluster) methods invoking the generalized Hellmann–Feynman theorem. In such a procedure, one constructs a functional which, besides the usual wave‐function parameters, contains new ones. One set of stationary conditions will reproduce exactly the original equations of the method, while the others will determine the value of the new parameters. We applied this straightforward procedure to derive analytic energy derivatives for several coupled‐cluster (CC) methods applicable to excited states such as the Hilbert‐space CC method, two‐determinetal (TD) CC method, Fock‐space CC method, and equation‐of‐motion–CC (EOM–CC) method. Finally, we compared the computational requirements for the different methods. © 1995 John Wiley & Sons, Inc.

UR - http://www.scopus.com/inward/record.url?scp=84987142324&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84987142324&partnerID=8YFLogxK

U2 - 10.1002/qua.560550210

DO - 10.1002/qua.560550210

M3 - Article

AN - SCOPUS:84987142324

VL - 55

SP - 151

EP - 163

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 2

ER -