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Journal of Physical Chemistry A
Volumn 112, Issue 15, 2008, Pages 3391-3398
Charge transfer and OH vibrational frequency red shifts in nitrate-water clusters
Author keywords

[No Author keywords available]
Indexed keywords

DOPPLER EFFECT; IONS; MOLECULES; NITRATES;
EID: 47049131893     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0761012     Document Type: Article
Times cited : (50)
References (87)
  • 24
  • 30
    • 47049090734 scopus 로고    scopus 로고
    • -1) is also lifted in the aqueous phase. However, the experiments indicate that this splitting becomes noticeable only when the anion concentration is very high, and is considered as a contact ion-pair formation indicator; see, for example, ref 9. Another signature is the appearance of the symmetric NO stretching mode in the IR spectrum, which is only Raman active in the gas phase.
    • -1) is also lifted in the aqueous phase. However, the experiments indicate that this splitting becomes noticeable only when the anion concentration is very high, and is considered as a contact ion-pair formation indicator; see, for example, ref 9. Another signature is the appearance of the symmetric NO stretching mode in the IR spectrum, which is only Raman active in the gas phase.
  • 41
    • 47049118765 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Bakken, V, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. L, Fox, D. J, Keit
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
  • 57
    • 47049110975 scopus 로고    scopus 로고
    • OHvalues, which were computed at the RHF level with the same basis.
    • OHvalues, which were computed at the RHF level with the same basis.
  • 59
    • 47049095431 scopus 로고    scopus 로고
    • In this connection, we note that MP2 energies were used in the DVR code. In addition, once sufficient ab initio points spanning the desired energy range were obtained, fine-graining of the potential, for the purpose of DVR convergence checks, was done via cubic spline interpolation.
    • In this connection, we note that MP2 energies were used in the DVR code. In addition, once sufficient ab initio points spanning the desired energy range were obtained, fine-graining of the potential, for the purpose of DVR convergence checks, was done via cubic spline interpolation.
  • 63
    • 47049108753 scopus 로고    scopus 로고
    • Though N3 appears to have two H-bonds, only one of the O⋯HO interactions falls within the standard H-bond geometric limits. The other one has too large an O⋯H distance (≈2.4 Å, and its OHO angle is much too bent ≈122°, Furthermore, the σ* OHpopulation for this OH stretch is only a tenth of that for the H-bonded OH
    • OHpopulation for this OH stretch is only a tenth of that for the H-bonded OH.
  • 64
    • 47049129806 scopus 로고    scopus 로고
    • 2O molecules and, hence, the symmetry set for the initial structure. All other degrees of freedom were allowed to freely adjust.
    • 2O molecules and, hence, the symmetry set for the initial structure. All other degrees of freedom were allowed to freely adjust.
  • 66
    • 47049115456 scopus 로고    scopus 로고
    • The motion corresponding to the imaginary frequency in N1 is the outer OH wag about the H-bond axis.
    • The motion corresponding to the imaginary frequency in N1 is the outer OH wag about the H-bond axis.
  • 67
    • 0003450764 scopus 로고    scopus 로고
    • National Institute of Standards and Technology: Gaithersburg, MD
    • NIST Standard Reference Database Number 69; National Institute of Standards and Technology: Gaithersburg, MD, 2005.
    • (2005) NIST Standard Reference Database Number 69
  • 68
    • 47049083348 scopus 로고    scopus 로고
    • -, which exhibits a dramatically large OH red shift in its one-water complex.
    • -, which exhibits a dramatically large OH red shift in its one-water complex.
  • 73
    • 47049087976 scopus 로고    scopus 로고
    • - often report the X-O coordination number in the approximate range of 5-7. This number is expected to be slightly larger than its X-H counterpart based on neutron diffraction measurements, such as ref 41.
    • - often report the X-O coordination number in the approximate range of 5-7. This number is expected to be slightly larger than its X-H counterpart based on neutron diffraction measurements, such as ref 41.
  • 76
    • 47049131826 scopus 로고    scopus 로고
    • One expects numerous intermolecular water-water H-bonds in the immediate vicinity of the studied anions in the solution phase. In the present anion-water CT context, such H-bonds will likely introduce difficulties into the interpretation of results owing to the cooperativity effect; see, for example, ref 32. On the other hand, such H-bond structures can induce an asymmetric local environment around an anion, an aspect of particular relevance to NO 3- in solution in connection with symmetry breaking
    • - in solution in connection with "symmetry breaking".
  • 78
    • 47049116492 scopus 로고    scopus 로고
    • In addition to the red shifts in Table 1, the reduced CT q w is also reflected in an increase in the (Ad-O w) distances, Ad being the anion donor site. Thompson and Hynes have shown that the anion-water separation is an important factor in determining the extent of CT and related effects for X-·H 2O (ref 19, for example, it is key for the large CT in F -·H2O. The Table 1 data extend their reasoning to larger clusters, providing a measure of sensitivity of the H-bond properties to the r(Ad-Ow) changes
    • w) changes.
  • 79
    • 47049089484 scopus 로고    scopus 로고
    • Kim and coworkers employed halide-water clusters with up to six waters, chosen based on their stability for a given number (n) of waters ref 23, Several structures contain H2O-H2O H-bonds, which we have avoided in the present work. Owing to the surface-like ion location in these clusters, the number of H2O's directly H-bonded to the halide is less than n in some cases, particularly for n, 5, 6. Thus, while the anion increasingly loses charge to surrounding waters as their count increases, it is clearly not split into n parts. The CT and the resulting OH red shift are strongly dependent on the structure, and detailed comparison is difficult
    • 2O's directly H-bonded to the halide is less than n in some cases, particularly for n = 5, 6. Thus, while the anion increasingly loses charge to surrounding waters as their count increases, it is clearly not split into n parts. The CT and the resulting OH red shift are strongly dependent on the structure, and detailed comparison is difficult.
  • 80
    • 47049128352 scopus 로고    scopus 로고
    • q on them may arise from the Coulombic polarization stage itself.
    • q on them may arise from the Coulombic polarization stage itself.
  • 87
    • 85052275592 scopus 로고    scopus 로고
    • - are listed in the NIST database (ref 38). For Figure 3, we have used a rough average value of 1370 kJ/mol.
    • - are listed in the NIST database (ref 38). For Figure 3, we have used a rough average value of 1370 kJ/mol.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.