Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Accurate multireference configuration interaction calculations on the lowest 1Σ+ and 3Π electronic states of C2, CN+, BN, and BO+

Abstract

In this study, using a series of correlation consistent basis sets from double to quintuple zeta in conjunction with large internally contracted multireference configuration interaction (CMRCI) wave functions, potential energy functions have been computed for the X1Σ+g and a 3Πu states of C2 and the 1 1Σ+ and 1 3Π states of CN+, BN, and BO+. By exploiting the regular convergence behavior of the correlation consistent basis sets, complete basis set limits have been estimated that led to accurate predictions for the electronic excitation energies, dissociation energies, equilibrium bond lengths, and harmonic vibrational frequencies. The 1 1Σ+ states of CN+ and BO+ are predicted to be the electronic ground states of these species with predicted equilibrium excitation energies (Te) to the low-lying a 3Π states of 880±100 cm-1 and 5000±200 cm-1, respectively. A 3Π ground state of BN is predicted with an excitation energy to the low-lying a 1Σ+ state of just 190±100 cm-1. Identical calculations on the singlet–triplet splitting of C2 yielded a prediction of 778 cm-1 for Te, which was just 62 cm-1 above the experimental value. Accurate equilibrium bond lengths and fundamental frequencies are also predicted for BN, BO+, and the a 3Π state of CN+. Dipolemore » moment functions have been computed by CMRCI for the ground and excited electronic states of the three heteronuclear diatomics, and these have been used to derive accurate microwave and infrared transition probabilities for these species. A dipole moment in v=0 of 5.42 D is calculated for the X1Σ+ state of BO+, which should lead to an intense microwave spectrum. While the X 3Π ground state of BN is predicted to have a very weak infrared spectrum, this species should be observable in the microwave region since the predicted μ0 is 1.98 D. Lastly, both the microwave and infrared spectra of X 1Σ+ CN+ should be of moderate intensity.« less

Authors:
 [1]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1490336
Report Number(s):
PNL-SA-24357
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830; FG06-89ER75522
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 102; Journal Issue: 1; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Peterson, Kirk A. Accurate multireference configuration interaction calculations on the lowest 1Σ+ and 3Π electronic states of C2, CN+, BN, and BO+. United States: N. p., 1995. Web. doi:10.1063/1.469399.
Copy to clipboard
Peterson, Kirk A. Accurate multireference configuration interaction calculations on the lowest 1Σ+ and 3Π electronic states of C2, CN+, BN, and BO+. United States. https://doi.org/10.1063/1.469399
Copy to clipboard
Peterson, Kirk A. Sun . "Accurate multireference configuration interaction calculations on the lowest 1Σ+ and 3Π electronic states of C2, CN+, BN, and BO+". United States. https://doi.org/10.1063/1.469399. https://www.osti.gov/servlets/purl/1490336.
Copy to clipboard
@article{osti_1490336,
title = {Accurate multireference configuration interaction calculations on the lowest 1Σ+ and 3Π electronic states of C2, CN+, BN, and BO+},
author = {Peterson, Kirk A.},
abstractNote = {In this study, using a series of correlation consistent basis sets from double to quintuple zeta in conjunction with large internally contracted multireference configuration interaction (CMRCI) wave functions, potential energy functions have been computed for the X1Σ+g and a 3Πu states of C2 and the 1 1Σ+ and 1 3Π states of CN+, BN, and BO+. By exploiting the regular convergence behavior of the correlation consistent basis sets, complete basis set limits have been estimated that led to accurate predictions for the electronic excitation energies, dissociation energies, equilibrium bond lengths, and harmonic vibrational frequencies. The 1 1Σ+ states of CN+ and BO+ are predicted to be the electronic ground states of these species with predicted equilibrium excitation energies (Te) to the low-lying a 3Π states of 880±100 cm-1 and 5000±200 cm-1, respectively. A 3Π ground state of BN is predicted with an excitation energy to the low-lying a 1Σ+ state of just 190±100 cm-1. Identical calculations on the singlet–triplet splitting of C2 yielded a prediction of 778 cm-1 for Te, which was just 62 cm-1 above the experimental value. Accurate equilibrium bond lengths and fundamental frequencies are also predicted for BN, BO+, and the a 3Π state of CN+. Dipole moment functions have been computed by CMRCI for the ground and excited electronic states of the three heteronuclear diatomics, and these have been used to derive accurate microwave and infrared transition probabilities for these species. A dipole moment in v=0 of 5.42 D is calculated for the X1Σ+ state of BO+, which should lead to an intense microwave spectrum. While the X 3Π ground state of BN is predicted to have a very weak infrared spectrum, this species should be observable in the microwave region since the predicted μ0 is 1.98 D. Lastly, both the microwave and infrared spectra of X 1Σ+ CN+ should be of moderate intensity.},
doi = {10.1063/1.469399},
journal = {Journal of Chemical Physics},
number = 1,
volume = 102,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 1995},
month = {Sun Jan 01 00:00:00 EST 1995}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.469399
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 119 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A b i n i t i o study of boron, nitrogen, and boron–nitrogen clusters. I. Isomers and thermochemistry of B 3 , B 2 N, BN 2 , and N 3
journal, June 1989

  • Martin, J. M. L.; François, J. P.; Gijbels, R.
  • The Journal of Chemical Physics, Vol. 90, Issue 11
  • DOI: 10.1063/1.456313

A simple method for the evaluation of the second-order-perturbation energy from external double-excitations with a CASSCF reference wavefunction
journal, April 1982

Full configuration interaction benchmark calculations for transition moments
journal, January 1988

  • Bauschlicher, Charles W.; Langhoff, Stephen R.
  • Theoretica Chimica Acta, Vol. 73, Issue 1
  • DOI: 10.1007/BF00526649

Ab initio multireference study of the BN molecule
journal, November 1992

  • Martin, J. M. L.; Lee, Timothy J.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 97, Issue 9
  • DOI: 10.1063/1.463684

An experimental determination of the heat of formation of C2 and the CH bond dissociation energy in C2H
journal, March 1991

High-multiplicity states of BN and BN+ obtained by configuration-interaction studies
journal, February 1988

Configuration-interaction study of low-lying valence states of BO +
journal, August 1987

Theoretical study of the diatomic alkali and alkaline‐earth oxides
journal, April 1986

  • Langhoff, Stephen R.; Bauschlicher, Charles W.; Partridge, Harry
  • The Journal of Chemical Physics, Vol. 84, Issue 8
  • DOI: 10.1063/1.450019

Benchmark calculations with correlated molecular wave functions. IV. The classical barrier height of the H+H 2 →H 2 +H reaction
journal, May 1994

  • Peterson, Kirk A.; Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 100, Issue 10
  • DOI: 10.1063/1.466884

Ab initio CI study of CN + : the identity of the ground state
journal, October 1979

Ab initio spectroscopy and thermochemistry of the BN molecule
journal, March 1991

  • Martin, J. M. L.; Fran�ois, J. P.; Gijbels, R.
  • Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 21, Issue 1
  • DOI: 10.1007/BF01426617

A b i n i t i o calculations on C 2 , Si 2 , and SiC
journal, September 1987

  • Bauschlicher, Charles W.; Langhoff, Stephen R.
  • The Journal of Chemical Physics, Vol. 87, Issue 5
  • DOI: 10.1063/1.453080

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Theoretical prediction of the potential curves for the lowest‐lying states of the isovalent diatomics CN + , Si 2 , SiC, CP + , and SiN + using the a b i n i t i o MRD‐CI method
journal, May 1980

  • Bruna, Pablo J.; Peyerimhoff, Sigrid D.; Buenker, Robert J.
  • The Journal of Chemical Physics, Vol. 72, Issue 10
  • DOI: 10.1063/1.439012

The ground state of the CN+ ion: a multi-reference Ci study
journal, June 1980

A progress report on the status of the COLUMBUSMRCI program system
journal, March 1988

  • Shepard, Ron; Shavitt, Isaiah; Pitzer, Russell M.
  • International Journal of Quantum Chemistry, Vol. 34, Issue S22
  • DOI: 10.1002/qua.560340819

Accurate Quantum Chemical Calculations
book, January 1990

  • Bauschlicher, Jr., Charles W.; Langhoff, Stephen R.; Taylor, Peter R.
  • Advances in Chemical Physics: Prigogine/Advances, Vol. 77
  • DOI: 10.1002/9780470141267.ch3

Coupled‐cluster calculations on the C 2 molecule and the C + 2 and C − 2 molecular ions
journal, April 1992

  • Watts, John D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 96, Issue 8
  • DOI: 10.1063/1.462649

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Ab initio potential curves for the lowest 1Σ+ and 3Π states of the ion CN+
journal, August 1979

An efficient internally contracted multiconfiguration–reference configuration interaction method
journal, November 1988

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 89, Issue 9
  • DOI: 10.1063/1.455556

Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464303

A determinant based full configuration interaction program
journal, April 1989

Potential energy curves of the lower states of CN +
journal, December 1979

Benchmark calculations with correlated molecular wave functions. III. Configuration interaction calculations on first row homonuclear diatomics
journal, December 1993

  • Peterson, Kirk A.; Kendall, Rick A.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 99, Issue 12
  • DOI: 10.1063/1.465461

A second order multiconfiguration SCF procedure with optimum convergence
journal, June 1985

  • Werner, Hans‐Joachim; Knowles, Peter J.
  • The Journal of Chemical Physics, Vol. 82, Issue 11
  • DOI: 10.1063/1.448627

SCF potential energy curves of CN+. The identify of the ground state
journal, December 1978

Configuration interaction calculations on the nitrogen molecule
journal, January 1974

  • Langhoff, Stephen R.; Davidson, Ernest R.
  • International Journal of Quantum Chemistry, Vol. 8, Issue 1
  • DOI: 10.1002/qua.560080106

The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule
journal, February 1981

  • Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders
  • The Journal of Chemical Physics, Vol. 74, Issue 4
  • DOI: 10.1063/1.441359

General contraction of Gaussian atomic orbitals: Core, valence, polarization, and diffuse basis sets; Molecular integral evaluation
journal, May 1973

  • Raffenetti, Richard C.
  • The Journal of Chemical Physics, Vol. 58, Issue 10
  • DOI: 10.1063/1.1679007

Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides
journal, August 1993

  • Peterson, Kirk A.; Kendall, Rick A.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 99, Issue 3
  • DOI: 10.1063/1.465307

Experimental Identification of the Ground State of BN in a Rare‐Gas Matrix
journal, June 1970

  • Mosher, Oren A.; Frosch, R. P.
  • The Journal of Chemical Physics, Vol. 52, Issue 11
  • DOI: 10.1063/1.1672859

A theoretical study of the electronic transition moment for the C2 swan band system
journal, May 1978

  • Arnold, J. O.; Langhoff, S. R.
  • Journal of Quantitative Spectroscopy and Radiative Transfer, Vol. 19, Issue 5
  • DOI: 10.1016/0022-4073(78)90013-4

An efficient method for the evaluation of coupling coefficients in configuration interaction calculations
journal, April 1988

A CI procedure using SCF MOs as basis functions. Application to HNO and NCO+
journal, April 1977

An efficient second-order MC SCF method for long configuration expansions
journal, April 1985

Theoretical study of C 2 and C 2 −
journal, July 1980

  • Dupuis, M.; Liu, B.
  • The Journal of Chemical Physics, Vol. 73, Issue 1
  • DOI: 10.1063/1.439879

A CAS SCF CI study of the 1Σ+g and 3IIu states of the C2 molecule and the 4Σ−g and 2IIu states of the C+2 ion
journal, December 1987

A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980

Benchmark calculations with correlated molecular wave functions. VI. Second row A 2 and first row/second row AB diatomic molecules
journal, November 1994

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 101, Issue 10
  • DOI: 10.1063/1.468080

New analysis of the A3Πi-X3Πi transition of BN
journal, August 1985

Application of systematic sequences of wave functions to the water dimer
journal, April 1992

  • Feller, David
  • The Journal of Chemical Physics, Vol. 96, Issue 8
  • DOI: 10.1063/1.462652

Ab initio calculations of the electronic transition moments and radiative lifetimes in some BN band systems
journal, November 1988

Low‐Lying Valence Levels of BN and C 2 . The Ground State of BN
journal, January 1967

  • Verhaegen, G.; Richards, W. G.; Moser, C. M.
  • The Journal of Chemical Physics, Vol. 46, Issue 1
  • DOI: 10.1063/1.1840367

Singlet and triplet energy surfaces of NiH 2
journal, May 1983

  • Blomberg, M. R. A.; Siegbahn, P. E. M.
  • The Journal of Chemical Physics, Vol. 78, Issue 9
  • DOI: 10.1063/1.445449

Can the lowest two electronic states of Si2 be ordered?
journal, April 1987

The study of molecular spectroscopy by ab initio methods
journal, July 1991

  • Bauschlicher, Charles W.; Langhoff, Stephen R.
  • Chemical Reviews, Vol. 91, Issue 5
  • DOI: 10.1021/cr00005a004

Theoretical study of the electronic transition moment for the d 3IIga 3IIu band system of the C2 molecule
journal, October 1978

Theoretical estimate of the enthalpy of formation of sulfhydryl radical (HSO) and HSO-SOH isomerization energy
journal, January 1993

  • Xantheas, Sotiris S.; Dunning, Thom H.
  • The Journal of Physical Chemistry, Vol. 97, Issue 1
  • DOI: 10.1021/j100103a005

The singlet bands of BN
journal, January 1984

  • Bredohl, H.; Dubois, I.; Houbrechts, Y.
  • Journal of Physics B: Atomic and Molecular Physics, Vol. 17, Issue 1
  • DOI: 10.1088/0022-3700/17/1/015

The Ballik-Ramsay, Mulliken, Deslandres-d'Azambuja and Phillips systems in C2: a theoretical study of their electronic transition moments
journal, November 1983

Electronic rearrangements during chemical reactions. II. Planar dissociation of ethylene
journal, November 1979

  • Cheung, L. M.; Sundberg, K. R.; Ruedenberg, K.
  • International Journal of Quantum Chemistry, Vol. 16, Issue 5
  • DOI: 10.1002/qua.560160512

Ground and low-lying valence states of BN: A CI study
journal, September 1985

The dissociation energy of CN and C 2
journal, September 1994

  • Pradhan, Atul D.; Partridge, Harry; Bauschlicher, Charles W.
  • The Journal of Chemical Physics, Vol. 101, Issue 5
  • DOI: 10.1063/1.467503

A theoretical study of the isovalent diatomics carbon dimer, silicon dimer, and silicon monocarbide
journal, May 1986

  • Rohlfing, Celeste McMichael; Martin, Richard L.
  • The Journal of Physical Chemistry, Vol. 90, Issue 10
  • DOI: 10.1021/j100401a014

The valence states of C2: A configuration interaction study
journal, January 1979

  • Kirby, K.; Liu, B.
  • The Journal of Chemical Physics, Vol. 70, Issue 2
  • DOI: 10.1063/1.437480
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Quadruple bonding in C2 and analogous eight-valence electron species
    journal, January 2012

    • Shaik, Sason; Danovich, David; Wu, Wei
    • Nature Chemistry, Vol. 4, Issue 3
    • DOI: 10.1038/nchem.1263

    A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures
    journal, November 2008

    • Feller, David; Peterson, Kirk A.; Dixon, David A.
    • The Journal of Chemical Physics, Vol. 129, Issue 20
    • DOI: 10.1063/1.3008061

    Ab initio characterization of the structure and energetics of the ArHF complex
    journal, August 1997

    • van Mourik, Tanja; Dunning, Thom H.
    • The Journal of Chemical Physics, Vol. 107, Issue 7
    • DOI: 10.1063/1.475148

    Theoretical prediction on the structures and stability of the noble-gas containing anions FNgCC − (Ng=He, Ar, Kr, and Xe)
    journal, November 2012

    • Peng, Chia-Yu; Yang, Chang-Yu; Sun, Yi-Lun
    • The Journal of Chemical Physics, Vol. 137, Issue 19
    • DOI: 10.1063/1.4766326

    Accurate thermochemistry from explicitly correlated distinguishable cluster approximation
    journal, February 2015

    • Kats, Daniel; Kreplin, David; Werner, Hans-Joachim
    • The Journal of Chemical Physics, Vol. 142, Issue 6
    • DOI: 10.1063/1.4907591

    Vibrational and electronic collisional-radiative model in CO 2 -N 2 -Ar mixtures for Mars entry problems
    journal, October 2019

    • Annaloro, Julien; Bultel, Arnaud
    • Physics of Plasmas, Vol. 26, Issue 10
    • DOI: 10.1063/1.5114792

    C n ( n =2−4): current status
    journal, February 2018

    • Varandas, A. J. C.; Rocha, C. M. R.
    • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 376, Issue 2115
    • DOI: 10.1098/rsta.2017.0145

    Pure Rotational Spectrum of CN +
    journal, September 2019

      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: