TY - JOUR
T1 - Ab initio studies on the structures, vertical electron detachment energies, and stabilities of CnP- clusters
AU - Zhan, Chang Guo
AU - Iwata, Suehiro
PY - 1997/11/8
Y1 - 1997/11/8
N2 - In this work, the structures, vertical electron detachment energies and fragmentation energies of CnP- clusters (n = 1 to 7) have been investigated by carrying out the geometry optimizations with MP2 method using 6-31G(d) augmented with a set of diffuse s p functions followed by the energy calculations at higher levels. It can be concluded from our calculated results that for the ground states the linear structures are stable only for C2P- and C3P-. Other CnP- (n = 4 to 7) clusters are slightly bent, and the bent CnP- with odd n is very floppy for bending motion. The contributions of the bending of the structures of CnP- with odd n to the stability can be ignored, and therefore these clusters could appear pseudolinear in experiment. The calculated vertical electron detachment and fragmentation energies of CnP- (n = 1 to 7) in their ground states reveal that the CnP- clusters with odd n are more stable than those with even n, which is consistent with the observed odd-even alternation in the TOF signal intensities. It has been also found that the odd-even alternation in fragmentation energies of CnP- is weaker than that of CnN-. Therefore, the stability difference for CnP- between the odd n and even n is smaller than that for CnN-. This conclusion is also coincident with the experimental observation reported.
AB - In this work, the structures, vertical electron detachment energies and fragmentation energies of CnP- clusters (n = 1 to 7) have been investigated by carrying out the geometry optimizations with MP2 method using 6-31G(d) augmented with a set of diffuse s p functions followed by the energy calculations at higher levels. It can be concluded from our calculated results that for the ground states the linear structures are stable only for C2P- and C3P-. Other CnP- (n = 4 to 7) clusters are slightly bent, and the bent CnP- with odd n is very floppy for bending motion. The contributions of the bending of the structures of CnP- with odd n to the stability can be ignored, and therefore these clusters could appear pseudolinear in experiment. The calculated vertical electron detachment and fragmentation energies of CnP- (n = 1 to 7) in their ground states reveal that the CnP- clusters with odd n are more stable than those with even n, which is consistent with the observed odd-even alternation in the TOF signal intensities. It has been also found that the odd-even alternation in fragmentation energies of CnP- is weaker than that of CnN-. Therefore, the stability difference for CnP- between the odd n and even n is smaller than that for CnN-. This conclusion is also coincident with the experimental observation reported.
UR - http://www.scopus.com/inward/record.url?scp=0001283201&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0001283201&partnerID=8YFLogxK
U2 - 10.1063/1.474971
DO - 10.1063/1.474971
M3 - Article
AN - SCOPUS:0001283201
SN - 0021-9606
VL - 107
SP - 7323
EP - 7330
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 18
ER -