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A complete active space self-consistent field study of the photochemistry of nitrosamine
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10.1063/1.2360259
/content/aip/journal/jcp/125/16/10.1063/1.2360259
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/16/10.1063/1.2360259

Figures

Image of FIG. 1.
FIG. 1.

Relevant critical points of nitrosamine on the singlet surfaces. The arrows in the smaller figures correspond to (i) stationary points: imaginary modes, (ii) surface crossings: gradient difference and nonadiabatic coupling vectors; (a) minimum (Ml); [(b) and (c)] transition states for the NO rotation around the N–N bond (Sd1 and Sd2); (d) first order saddle point (Sd3); (e) first order saddle point (Sd4); (f) transition state for the N–N bond cleavage (Sd5); (g) conical intersection (Ci1); (h) minimum (M2); (i) minimum (M3); (j) first order saddle point (Sd6); (k) conical intersection (Ci2); (l) conical intersection (Ci2b); (m) conical intersection (Ci3); (n) conical intersection (Ci4); (o) intersystem crossing (Isc1).

Image of FIG. 2.
FIG. 2.

Energy profiles (MS-CASPT2) of the main dissociation channels of nitrosamine on the relevant low-lying singlet states. Initial and final geometries are represented on top of the vertical axis: (a) minimum (M1) to ; (b) dissociation transition state (Sd5) to ; (c) minimum (M1) to ; (d) minimum (M3) to . The electronic state of the products is presented at the end of the potential energy curves. The character of the states is indicated at the beginning of the curves.

Image of FIG. 3.
FIG. 3.

Critical points of nitrosamine related to its tautomers. The arrows in the smaller figures correspond to (i) stationary points: imaginary modes, (ii) surface crossings: gradient difference and nonadiabatic coupling vectors; (a) cis-hydroxydiimide minimum on (M4); (b) trans-hydroxydiimide minimum on (M5); (c) transition state for the 1,3-hydrogen shift (Sd7); (d) conical intersection (Ci5); (e) diimide-N-oxide minimum on (M6); (f) transition state for the 1,2-hydrogen shift (Sd8); (g) first order saddle point (Sd9); (h) diimide-N-oxide minimum on (M7).

Image of FIG. 4.
FIG. 4.

MS-CASPT2 potential energy profiles comparison between the adiabatic lowest energy channels on the ground state surface based on CAS-SCF(16,12) reference wave functions. The products are presented at the end of the correspondent curve. Transition states, if applicable, are indicated.

Image of FIG. 5.
FIG. 5.

Relevant critical points of nitrosamine on the first excited triplet state. The arrows in the smaller figures correspond to (i) stationary points: imaginary modes, (ii) surface crossings: gradient difference vectors; (a) minimum (M8); (b) minimum (M9); (c) nitrene minimum (M10); (d) second order saddle point (Sd10); [(e) and (f)] intersystem crossings (Isc2 and Isc3).

Image of FIG. 6.
FIG. 6.

MS-CASPT2 interpolations between M1 and the intersystem crossings: (a) Isc2; (b) Isc3. Initial and final geometries are represented on top of the vertical axis. The electronic state of the fragments is indicated at the end of each of the curves. The character of the states is indicated at the beginning of the curves.

Image of FIG. 7.
FIG. 7.

Energy diagram of the relevant critical points and chemical paths of nitrosamine photochemistry. stands for vertical transition, , for minimum, , for saddle point, , for conical intersection, and , for intersystem crossing, is an ordinal. Between parentheses (brackets) is indicated the relative energy value of the critical point (Franck-Condon point) in kcal/mol.The horizontal dotted lines represent the energy level of the correspondent vertical transition. The vertical arrows represent the main electronic absorptions and their wideness displays qualitatively the magnitude of the oscillator strength.

Tables

Generic image for table
Table I.

MS-CASPT2 energies of the singlet and triplet vertical transitions of nitrosamine.

Generic image for table
Table II.

MS-CASPT2 energies of the critical points of nitrosamine relevant to its photodecomposition on singlet states.

Generic image for table
Table III.

MS-CASPT2 energies of the critical points and their corresponding vertical transitions of the structures related to nitrosamine tautomers on the lowest relevant potential energy surfaces.

Generic image for table
Table IV.

MS-CASPT2 energies of the relevant critical points on the first triplet excited state of nitrosamine.

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/content/aip/journal/jcp/125/16/10.1063/1.2360259
2006-10-24
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A complete active space self-consistent field study of the photochemistry of nitrosamine
http://aip.metastore.ingenta.com/content/aip/journal/jcp/125/16/10.1063/1.2360259
10.1063/1.2360259
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