TY - JOUR
T1 - Nonrigid large van der Waals molecules
AU - Jortner, Joshua
AU - Ben-Horin, Narda
AU - Scharf, Daphna
PY - 1993/3
Y1 - 1993/3
N2 - We address the breakdown of the (nearly) rigid molecule description of molecular structure and spectra, which is realized when the amplitude of atomic motion becomes comparable with the average bond length. This situation prevails for van der Waals molecules and clusters at finite temperatures. Molecular nonrigidity was characterized in terms of an "intramolecular melting" Lindemann criterion, which reveals that aromatic molecule (M)-rare gas (A≡Ar, Kr, Xe) van der Waals molecules (clusters) are nonrigid at T≥10 K. A quantification of the concept of molecular nonrigidity in these systems was provided by constant energy molecular dynamics simulations for the smallest cluster of the M·An family, i.e., the one-sided (2|0) benzene · Ar2 molecule, which reveals a hierarchy of isomerization phenomena with increasing temperature.
AB - We address the breakdown of the (nearly) rigid molecule description of molecular structure and spectra, which is realized when the amplitude of atomic motion becomes comparable with the average bond length. This situation prevails for van der Waals molecules and clusters at finite temperatures. Molecular nonrigidity was characterized in terms of an "intramolecular melting" Lindemann criterion, which reveals that aromatic molecule (M)-rare gas (A≡Ar, Kr, Xe) van der Waals molecules (clusters) are nonrigid at T≥10 K. A quantification of the concept of molecular nonrigidity in these systems was provided by constant energy molecular dynamics simulations for the smallest cluster of the M·An family, i.e., the one-sided (2|0) benzene · Ar2 molecule, which reveals a hierarchy of isomerization phenomena with increasing temperature.
KW - "Intramolecular melting" Lindemann criterion
KW - Nonrigidity
KW - Van der Waals molecules
UR - http://www.scopus.com/inward/record.url?scp=3343009092&partnerID=8YFLogxK
U2 - 10.1007/BF01374588
DO - 10.1007/BF01374588
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AN - SCOPUS:3343009092
SN - 1432-881X
VL - 85
SP - 199
EP - 207
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 1-3
ER -