Scaled Second Order Perturbation Corrections to Configuration Interaction Singles: Efficient and Reliable Excitation Energy Methods

PDF Version Also Available for Download.

Description

Two modifications of the perturbative doubles correction to configuration interaction with single substitutions (CIS(D)) are suggested, which are excited state analogs of ground state scaled second order Moeller-Plesset (MP2) methods. The first approach employs two parameters to scale the two spin components of the direct term of CIS(D), starting from the two-parameter spin-component scaled (SCS) MP2 ground state, and is termed SCS-CIS(D). An efficient resolution-of-the-identity (RI) implementation of this approach is described. The second approach employs a single parameter to scale only the opposite-spin direct term of CIS(D), starting from the one-parameter scaled opposite spin (SOS) MP2 ground state, and ... continued below

Physical Description

49

Creation Information

Rhee, Young Min & Head-Gordon, Martin February 1, 2007.

Context

This article is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this article can be viewed below.

Who

People and organizations associated with either the creation of this article or its content.

Publisher

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this article. Follow the links below to find similar items on the Digital Library.

Description

Two modifications of the perturbative doubles correction to configuration interaction with single substitutions (CIS(D)) are suggested, which are excited state analogs of ground state scaled second order Moeller-Plesset (MP2) methods. The first approach employs two parameters to scale the two spin components of the direct term of CIS(D), starting from the two-parameter spin-component scaled (SCS) MP2 ground state, and is termed SCS-CIS(D). An efficient resolution-of-the-identity (RI) implementation of this approach is described. The second approach employs a single parameter to scale only the opposite-spin direct term of CIS(D), starting from the one-parameter scaled opposite spin (SOS) MP2 ground state, and is called SOS-CIS(D). By utilizing auxiliary basis expansions and a Laplace transform, a fourth order algorithm for SOS-CIS(D) is described and implemented. The parameters describing SCS-CIS(D) and SOS-CIS(D) are optimized based on a training set including valence excitations of various organic molecules and Rydberg transitions of water and ammonia, and they significantly improve upon CIS(D) itself. The accuracy of the two methods is found to be comparable. This arises from a strong correlation between the same-spin and opposite-spin portions of the excitation energy terms. The methods are successfully applied to the zincbacteriochlorin-bacteriochlorin charge transfer transition, for which time-dependent density functional theory, with presently available exchange-correlation functionals, is known to fail. The methods are also successfully applied to describe various electronic transitions outside of the training set. The efficiency of SOS-CIS(D) and the auxiliary basis implementation of CIS(D) and SCS-CIS(D) are confirmed with a series of timing tests.

Physical Description

49

Source

  • Journal Name: Journal of Physical Chemistry

Language

Item Type

Identifier

Unique identifying numbers for this article in the Digital Library or other systems.

  • Report No.: LBNL-1595E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 949213
  • Archival Resource Key: ark:/67531/metadc925761

Collections

This article is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

Office of Scientific and Technical Information (OSTI) is the Department of Energy (DOE) office that collects, preserves, and disseminates DOE-sponsored research and development (R&D) results that are the outcomes of R&D projects or other funded activities at DOE labs and facilities nationwide and grantees at universities and other institutions.

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • February 1, 2007

Added to The UNT Digital Library

  • Nov. 13, 2016, 7:26 p.m.

Description Last Updated

  • Nov. 18, 2016, 3:21 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 1

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Rhee, Young Min & Head-Gordon, Martin. Scaled Second Order Perturbation Corrections to Configuration Interaction Singles: Efficient and Reliable Excitation Energy Methods, article, February 1, 2007; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc925761/: accessed April 24, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.