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Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study
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10.1063/1.3685891
/content/aip/journal/jcp/136/8/10.1063/1.3685891
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/8/10.1063/1.3685891

Figures

Image of FIG. 1.
FIG. 1.

Energy diagram for ground electronic state dissociation and isomerization of hydroxymethyl radical. All energies are relative to CH2OH (CD2OH) vibrational ground state and calculated at RCCSD(T)/CBS level of theory using RCCSD(T)/AVTZ harmonic zero-point energies. For a quantitative comparison with the most recent experimental measurements of dissociation energies the ZPEs of CH2OH (CD2OH) and its dissociation products are calculated also using VSCF/VCI. These values are given in parentheses. Corresponding imaginary frequencies are indicated below the barriers. Note the lower barrier for dissociation of CH3O relative to CH2OH, and the comparable barriers for OH bond fission and isomerization in CH2OH.

Image of FIG. 2.
FIG. 2.

RCCSD(T)/AVTZ geometries for relevant stationary points of the CH2OH PES. All structures, except the CH2OH minimum (a), have C s symmetry. Bond lengths are in angstroms, dihedral angles are shown in square brackets. CH2O parameters: r CO = 1.208  Å, r CH = 1.102  Å, ∠COH = 121.7°.

Image of FIG. 3.
FIG. 3.

Contour plot showing the potential energy as a function of the OH bond length and the HOCH' dihedral angle (that equals 22° at the equilibrium geometry, (1)) with all other degrees of freedom relaxed. Dissociation without relaxation of the indicated torsional angle, (2), results in a barrier almost 4000 cm−1 above the saddle point, (3). Energy increases from blue to red and orange, interval between countor lines is 1000 cm−1.

Image of FIG. 4.
FIG. 4.

Frontier MOs (SOMO, HOMO-1, and HOMO-2) at the selected geometries of Fig. 3: equilibrium (a), a structure with the stretched OH bond and the HOCH' angle fixed at the equilibrium value (b), and the TS (c).

Tables

Generic image for table
Table I.

CH2OH spectroscopic parameters and zero-point energies (in cm−1) from VCI calculations. Vibrational mode descriptions are approximate; the mixed states in CH2OH are denoted by leading contributions in their VCI wavefunctions.

Generic image for table
Table II.

CD2OH spectroscopic parameters and zero-point energies (in cm−1) from VCI calculations.

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/content/aip/journal/jcp/136/8/10.1063/1.3685891
2012-02-24
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Overtone-induced dissociation and isomerization dynamics of the hydroxymethyl radical (CH2OH and CD2OH). I. A theoretical study
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/8/10.1063/1.3685891
10.1063/1.3685891
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