2017
DOI: 10.1063/1.4979909
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Nature of the valence excited states of bromine in the T and P clathrate cages

Abstract: The guest-host intermolecular potentials for the valence excited states of Br in the tetrakaidecahedral(T) and pentakaidecahedral(P) clathrate cages have been calculated using ab initio local correlation methods. We find that the excited states are more strongly bound than the corresponding ground states even in the small T cage where bromine has a tight fit. The angular dependence of the interaction energies is quite anisotropic; this reflects in the corresponding electronic shifts where regions of maxima for… Show more

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Cited by 6 publications
(37 citation statements)
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“…In particular the role of the ionic component as indicator of halogen bonding was stressed. This was further confirmed by performing a more thorough calculation of the electronic shifts taking into account the rotational motion of the dihalogen inside the cages . Another important set of experiments probed the structural characteristics of chlorine and bromine clathrates in X‐ray measurements .…”
Section: Introductionmentioning
confidence: 80%
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“…In particular the role of the ionic component as indicator of halogen bonding was stressed. This was further confirmed by performing a more thorough calculation of the electronic shifts taking into account the rotational motion of the dihalogen inside the cages . Another important set of experiments probed the structural characteristics of chlorine and bromine clathrates in X‐ray measurements .…”
Section: Introductionmentioning
confidence: 80%
“…This was further confirmed by performing a more thorough calculation of the electronic shifts taking into account the rotational motion of the dihalogen inside the cages. [14] Another important set of experiments probed the structural characteristics of chlorine and bromine clathrates in Xray measurements. [5] The case of chlorine has a long and interesting history starting with its accidental discovery by sir Humphrey Davy [15] in 1811, followed by the first X-ray determination in 1952 by Pauling and Marsh [16] where using van der Waals radii arguments it was assumed that chlorine would not fit in the smaller dodecahedral cage and the recent detailed study by the group of Ripmeester showing that more than 30 % of the 5 12 dodecahedral cages are occupied [5] .…”
Section: Introductionmentioning
confidence: 99%
“…The geometry of the water in each cage was fixed according to their experimental values 6,7,30,31 in the TS-I and CS-II structures as has been done in all of our previous studies. 9,12,13 The oxygen positions were obtained in X-ray experiments and the hydrogen atoms are arranged as to yield cages with low values of the dipole moment. 32 The halogen molecule was positioned in the center of the cage and its intramolecular distance was fixed to the optimal value in the isolated diatomic as provided by the DF-LMP2/AVTZ level of theory (2.29 Å).…”
Section: Geometry and Inclusion Energymentioning
confidence: 99%
“…Although the local methods make an important reduction 12,13,28 of the basis set superposition error (BSSE), the presence of several water molecules led to a non-negligible BSSE, and for this reason, we have applied the usual counterpoise procedure. 35,36 We report total inclusion energies at the DF-LCC2 level of theory.…”
Section: Geometry and Inclusion Energymentioning
confidence: 99%
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