Details
| Original language | English |
|---|---|
| Pages (from-to) | 145-153 |
| Number of pages | 9 |
| Journal | Chemical Physics |
| Volume | 199 |
| Issue number | 2-3 |
| Publication status | Published - 15 Oct 1995 |
| Externally published | Yes |
Abstract
The n → π* electronic transition (1 1A1 → 1 1A1) of formaldehyde solvated by a varying number of water molecules is investigated using multi-reference CI calculations. The water molecules are considered as spectator groups and are represented by an effective potential. The orthogonality between the wavefunctions of the spectators and the active part of the total system is maintained by employing basis sets for the active part of the spectator which do not significantly overlap. The spectator potential has also been generated in a semiempirical NDDO calculation with negligible loss of accuracy compared to a full ab initio spectator treatment. The calculated solvent shift agrees very well with corresponding results of the reference calculations which consider all water molecules explicitly. The presented combination of sophisticated correlation methods for the region of interest, and semiempirical methods to include the effect of the surroundings allows for fast and reliable calculations of solvent effects in large systems.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Chemical Physics, Vol. 199, No. 2-3, 15.10.1995, p. 145-153.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - The solvent shift in the n → π* excitation of CH2O · nH2O
T2 - An MRD-CI investigation using effective potentials for the representation of the water molecules
AU - Frank, Irmgard
AU - Grimme, Stefan
AU - von Arnin, Malte
AU - Peyerimhoff, Sigrid D.
PY - 1995/10/15
Y1 - 1995/10/15
N2 - The n → π* electronic transition (1 1A1 → 1 1A1) of formaldehyde solvated by a varying number of water molecules is investigated using multi-reference CI calculations. The water molecules are considered as spectator groups and are represented by an effective potential. The orthogonality between the wavefunctions of the spectators and the active part of the total system is maintained by employing basis sets for the active part of the spectator which do not significantly overlap. The spectator potential has also been generated in a semiempirical NDDO calculation with negligible loss of accuracy compared to a full ab initio spectator treatment. The calculated solvent shift agrees very well with corresponding results of the reference calculations which consider all water molecules explicitly. The presented combination of sophisticated correlation methods for the region of interest, and semiempirical methods to include the effect of the surroundings allows for fast and reliable calculations of solvent effects in large systems.
AB - The n → π* electronic transition (1 1A1 → 1 1A1) of formaldehyde solvated by a varying number of water molecules is investigated using multi-reference CI calculations. The water molecules are considered as spectator groups and are represented by an effective potential. The orthogonality between the wavefunctions of the spectators and the active part of the total system is maintained by employing basis sets for the active part of the spectator which do not significantly overlap. The spectator potential has also been generated in a semiempirical NDDO calculation with negligible loss of accuracy compared to a full ab initio spectator treatment. The calculated solvent shift agrees very well with corresponding results of the reference calculations which consider all water molecules explicitly. The presented combination of sophisticated correlation methods for the region of interest, and semiempirical methods to include the effect of the surroundings allows for fast and reliable calculations of solvent effects in large systems.
UR - http://www.scopus.com/inward/record.url?scp=0011773987&partnerID=8YFLogxK
U2 - 10.1016/0301-0104(95)00223-B
DO - 10.1016/0301-0104(95)00223-B
M3 - Article
AN - SCOPUS:0011773987
VL - 199
SP - 145
EP - 153
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
IS - 2-3
ER -