Computational study of the rovibrational spectrum of (CO2)2

Wang, Xiaogang; Carrington, Tucker; Dawes, Richard

doi:10.1016/j.jms.2016.08.006

Cited by 29 publications

(29 citation statements)

References 52 publications

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“…[21] Data for the final high-level PES was generated using the CCSD(T)-F12b/VTZ-F12 method and basis set. [22] The 4-D PES was constructed using an automated interpolating moving least squares method, which has been used in several previous studies [15,[23][24][25] and has been recently released as a software package under the name AUTOSURF. [26,27] This interpolative approach can accommodate arbitrary energy-surface topographies and is particularly advantageous in cases with large anisotropy, which are challenging for traditional Legendre expansions.…”

Section: Imls Pes Fittingmentioning

confidence: 99%

Computational study of the ro-vibrational spectrum of CO–CO2

Castro-Juárez

Wang

Carrington

et al. 2019

The Journal of Chemical Physics

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Section: Imls Pes Fittingmentioning

confidence: 99%

Computational study of the ro-vibrational spectrum of CO–CO2

Castro-Juárez

Wang

Carrington

et al. 2019

The Journal of Chemical Physics

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“…However, the application of CCSD(T) to systems with more than tens of electrons is prohibitively expensive. Thus, addressing even moderately sized CO 2 systems at chemical accuracy is challenging and an ongoing area of research …”

Section: Introductionmentioning

confidence: 99%

“…Many recent theoretical efforts have been undertaken to address these moderately sized systems, mostly on the carbon dioxide dimer, (CO 2 ) 2 , and trimer, (CO 2 ) 3 . In particular, Carrington and coworkers have recently studied the rovibrational spectrum of the dimer with coupled cluster theory near the complete basis set (CBS) limit . Beyond the dimer, discrepancies still exist in the literature regarding the relative stability of clusters, in particular the trimer.…”

Section: Introductionmentioning

confidence: 99%

Development of a Flexible‐Monomer Two‐Body Carbon Dioxide Potential and Its Application to Clusters up to (CO₂)₁₃

Sode

Cherry

2017

J Comput Chem

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A flexible-monomer two-body potential energy function was developed that approaches the high level CCSD(T)/CBS potential energy surface (PES) of carbon dioxide (CO ) systems. This function was generated by fitting the electronic energies of unique CO monomers and dimers to permutationally invariant polynomials. More than 200,000 CO configurations were used to train the potential function. Comparisons of the PESs of six orientations of flexible CO dimers were evaluated to demonstrate the accuracy of the potential. Furthermore, the potential function was used to determine the minimum energy structures of CO clusters containing as many as 13 molecules. For isomers of (CO ) , the potential demonstrated energetic agreement with the M06-2X functional and structural agreement of the B2PLYP-D functional at substantially reduced computational costs. A separate function, fit to MP2/aug-cc-pVDZ reference energies, was developed to directly compare the two-body potential to the ab initio MP2 level of theory. © 2017 Wiley Periodicals, Inc.

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“…Geared and anti-geared cycles are prominent on the PESs of many dimers. 21,22,25,26 However, the cycle is different in the CO-CO 2 case because the minima are not slipped parallel but T-shaped. The geometries and energies relative to the dissociation energy of the minima are given in Table I.…”

mentioning

confidence: 99%

“…18 Data for the final high-level PES was generated using the CCSD(T)-F12b/VTZ-F12 method and basis set. 19 The 4-D PES was constructed using an automated interpolating moving least squares method, which has been used in several previous studies 12,[20][21][22] and has been recently released as a software package under the name AUTOSURF. 23,24 This interpolative approach can accommodate arbitrary energy-surface topographies and is particularly advantageous in cases with large anisotropy, which are challenging for traditional Legendre expansions.…”

mentioning

confidence: 99%

Computational Study of the Ro-Vibrational Spectrum of CO-CO2

Castro-Juárez¹,

Wang²,

Carrington

et al. 2019

Preprint

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An accurate ab initio ground-state intermolecular potential energy surface (PES) was determined for the CO-CO 2 Van der Waals dimer. The Lanczos algorithm was used to compute ro-vibrational energies on this PES. For both the C-in and the O-in T-shaped isomers, the fundamental transition frequencies agree well with previous experimental results. We confirm that the in-plane states previously observed are geared states. In addition, we have computed and assigned many other vibrational states. The rotational constants we determine from J = 1 energy levels agree well with their experimental counterparts. Planar and out-ofplane cuts of some of the wavefunctions we compute are quite different, indicating strong coupling between the bend and torsional modes. Because the stable isomers are T-shaped, vibration along the out-of-plane coordinates is very floppy. In CO-CO 2 , when the molecule is out-of-plane, interconversion of the isomers is possible, but the barrier height is higher than the in-plane geared barrier height. I. INTRODUCTIONCO-CO 2 is a Van der Waals dimer composed of the two monomers CO and CO 2 , both of which are of astrophysical interest. Its infra-red and microwave spectra have been recorded and its structure determined. 1-3 CO-CO 2 has two stable isomers. Both are T-shaped with the CO 2 monomer at the top of the T and the CO monomer the stem of the T. The lower-energy isomer has the C of CO close to the C of CO 2 . The higher-energy isomer has the O of CO close to the C of CO 2 . We shall refer to these isomers as C-in and O-in. Both isomers are shown on the right side of Figure 1. The C-in isomer was first studied by Legon and Suckley 1 and later by others. 4,5 The existence of the O-in isomer was predicted by ab initio calculations 6 and later confirmed. 2 For both isomers, two inter-monomer transition frequencies have been observed. One is for an in-plane state and the other for an out-of-plane state. 2,3 Harmonic frequencies have also been computed with ab initio methods. 5-7 Although the experimental frequencies for the lower energy C-in isomer are rather close to the ab initio harmonic frequencies, the experimental O-in frequencies are not close to the harmonic values. In the C-in case, the agreement is good enough that the experimental in-plane vibration was assigned to the "CO rock/geared bend".In this paper, we report a new four-dimensional (4-D) ab initio potential energy surface (PES) that is a function of the intermolecular coordinates of CO-CO 2 , and energy levels computed on it. The PES is built using points computed at the CCSD(T)-F12b/VTZ-F12 level. The only approximation in the energy-level calculation is the separation of the high frequency intra-monomer coordinates from the low frequency inter-monomer coordinates. Energy levels and wavefunctions are computed with the Lanczos method and a large spherical-harmonic type basis. It has been demonstrated that such calculations are accurate for other Van der Waals dimers. 8-11 Probability Density (PD) and wavefunction cut plots are used to...

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Computational study of the rovibrational spectrum of (CO2)2

Cited by 29 publications

References 52 publications

Computational study of the ro-vibrational spectrum of CO–CO2

Computational study of the ro-vibrational spectrum of CO–CO2

Development of a Flexible‐Monomer Two‐Body Carbon Dioxide Potential and Its Application to Clusters up to (CO₂)₁₃

Computational Study of the Ro-Vibrational Spectrum of CO-CO2

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Computational study of the rovibrational spectrum of (CO2)2

Cited by 29 publications

References 52 publications

Computational study of the ro-vibrational spectrum of CO–CO2

Computational study of the ro-vibrational spectrum of CO–CO2

Development of a Flexible‐Monomer Two‐Body Carbon Dioxide Potential and Its Application to Clusters up to (CO2)13

Computational Study of the Ro-Vibrational Spectrum of CO-CO2

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Development of a Flexible‐Monomer Two‐Body Carbon Dioxide Potential and Its Application to Clusters up to (CO₂)₁₃