Multireference Methods for Calculating the Dissociation Enthalpy of Tetrahedral P4 to Two P2

Meagan S. Oakley, Jie J. Bao, Mariusz Klobukowski, Donald G Truhlar, Laura Gagliardi

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The potential energy surface for the thermal decomposition of P4 → 2P2 was computed along the C2v reaction trajectory. Single-reference methods were not suitable for describing this complex bond-breaking process, so two multiconfigurational methods, namely, multistate complete active space second-order perturbation theory (MS-CASPT2) and multiconfiguration pair-density functional theory (MC-PDFT), were used with the aim of determining the accuracy and efficiency of these methods for this process. Several active spaces and basis sets were explored. It was found that the multiconfiguration pair-density functional theory method was up to 900 times faster than multistate complete active space second-order perturbation theory while providing similar accuracy.

Original languageEnglish (US)
Pages (from-to)5742-5749
Number of pages8
JournalJournal of Physical Chemistry A
Volume122
Issue number26
DOIs
StatePublished - Jul 5 2018

Fingerprint

Density functional theory
Enthalpy
enthalpy
dissociation
Potential energy surfaces
perturbation theory
density functional theory
Pyrolysis
Trajectories
thermal decomposition
potential energy
trajectories

PubMed: MeSH publication types

  • Journal Article

Cite this

Multireference Methods for Calculating the Dissociation Enthalpy of Tetrahedral P4 to Two P2 . / Oakley, Meagan S.; Bao, Jie J.; Klobukowski, Mariusz; Truhlar, Donald G; Gagliardi, Laura.

In: Journal of Physical Chemistry A, Vol. 122, No. 26, 05.07.2018, p. 5742-5749.

Research output: Contribution to journalArticle

@article{3c25019e14e349578f588665e2062dab,
title = "Multireference Methods for Calculating the Dissociation Enthalpy of Tetrahedral P4 to Two P2",
abstract = "The potential energy surface for the thermal decomposition of P4 → 2P2 was computed along the C2v reaction trajectory. Single-reference methods were not suitable for describing this complex bond-breaking process, so two multiconfigurational methods, namely, multistate complete active space second-order perturbation theory (MS-CASPT2) and multiconfiguration pair-density functional theory (MC-PDFT), were used with the aim of determining the accuracy and efficiency of these methods for this process. Several active spaces and basis sets were explored. It was found that the multiconfiguration pair-density functional theory method was up to 900 times faster than multistate complete active space second-order perturbation theory while providing similar accuracy.",
author = "Oakley, {Meagan S.} and Bao, {Jie J.} and Mariusz Klobukowski and Truhlar, {Donald G} and Laura Gagliardi",
year = "2018",
month = "7",
day = "5",
doi = "10.1021/acs.jpca.7b12366",
language = "English (US)",
volume = "122",
pages = "5742--5749",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "26",

}

TY - JOUR

T1 - Multireference Methods for Calculating the Dissociation Enthalpy of Tetrahedral P4 to Two P2

AU - Oakley, Meagan S.

AU - Bao, Jie J.

AU - Klobukowski, Mariusz

AU - Truhlar, Donald G

AU - Gagliardi, Laura

PY - 2018/7/5

Y1 - 2018/7/5

N2 - The potential energy surface for the thermal decomposition of P4 → 2P2 was computed along the C2v reaction trajectory. Single-reference methods were not suitable for describing this complex bond-breaking process, so two multiconfigurational methods, namely, multistate complete active space second-order perturbation theory (MS-CASPT2) and multiconfiguration pair-density functional theory (MC-PDFT), were used with the aim of determining the accuracy and efficiency of these methods for this process. Several active spaces and basis sets were explored. It was found that the multiconfiguration pair-density functional theory method was up to 900 times faster than multistate complete active space second-order perturbation theory while providing similar accuracy.

AB - The potential energy surface for the thermal decomposition of P4 → 2P2 was computed along the C2v reaction trajectory. Single-reference methods were not suitable for describing this complex bond-breaking process, so two multiconfigurational methods, namely, multistate complete active space second-order perturbation theory (MS-CASPT2) and multiconfiguration pair-density functional theory (MC-PDFT), were used with the aim of determining the accuracy and efficiency of these methods for this process. Several active spaces and basis sets were explored. It was found that the multiconfiguration pair-density functional theory method was up to 900 times faster than multistate complete active space second-order perturbation theory while providing similar accuracy.

UR - http://www.scopus.com/inward/record.url?scp=85048219706&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85048219706&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.7b12366

DO - 10.1021/acs.jpca.7b12366

M3 - Article

VL - 122

SP - 5742

EP - 5749

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 26

ER -