Nuclear magnetic resonance parameters in water dimer
- 145 Downloads
The changes in the computed nuclear magnetic resonance (NMR) parameters of the water dimer with respect to their monomer values were monitored as the geometry of the dimer was systematically varied. Nuclear magnetic shielding constants, shielding tensor anisotropies, nuclear quadrupole coupling constants and spin–spin coupling constants for the hydrogen bond donor and acceptor molecules were calculated at hybrid density-functional theory level. The dimer geometry was specified through the intermolecular oxygen–oxygen distance R OO and the hydrogen bond angle α. A grid of 120 geometries was selected by systematically varying these two parameters. The other geometrical parameters of the dimer were allowed to relax, keeping the two parameters fixed. As the dimer geometry was varied, all NMR parameters were observed to be smoothly behaving. Characteristic changes as a function of the intermolecular geometry were observed. These include, besides the well-known deshielding of the donor hydrogen shielding constant, also influences on the donor deuterium quadrupole coupling constant, as well as the shielding anisotropy of the donor and acceptor oxygens. We discuss the contributions to the total dimerisation effect from, on the one hand, the dominant direct interaction effect at a fixed geometry and, on the other hand, from the quantitatively relevant indirect, geometric effect. A fundamental ambiguity of this partitioning is demonstrated. By forging the general, smooth trends in all the studied NMR parameters into a specific geometric definition, we find our data to be in agreement with the widely used distance criterion for hydrogen bonding in water, R OO ≤ 3.5 Å.
KeywordsHydrogen bonding Nuclear shielding Quadrupole coupling Spin–spin coupling Property surfaces Density-functional theory Direct and indirect interaction effects
TP is grateful to the financial support from the Graduate School of Computational Chemistry and Molecular Spectroscopy, Oulu University Scholarship Foundation, Research Foundation of Orion Corporation, The Finnish Foundation for Economic and Technology Sciences—KAUTE, Magnus Ehrnrooth Foundation, and Finnish Cultural Foundation. The authors belong to the Finnish Center of Excellence in Computational Molecular Science (CMS, 2006-11). PL is Academy Research Fellow of the Academy of Finland. Computational resources were partially provided by CSC—Scientific Computing Ltd, Espoo, Finland.
- 3.Eisenberg D, Kauzmann W (1969) The structure and properties of water. Clarendon, OxfordGoogle Scholar
- 9.Dyke TR (1984) Top Curr Chem 120:85Google Scholar
- 10.Halkier A, Koch H, Jørgensen P, Christiansen O, Nielsen IMB, Helgaker T (1997) Theor Chem Acc 97:150Google Scholar
- 13.Levitt MH (2001) Spin dynamics: basics of nuclear magnetic resonance. Wiley, ChichesterGoogle Scholar
- 15.Wigglesworth RD, Raynes WT, Sauer SPA, Oddershede J (1998) Mol Phys 94:851Google Scholar
- 17.Pennanen TS, Vaara J, Lantto P, Sillanpää AJ, Laasonen K, Jokisaari J (2004) J Am Chem Soc 126:11093, and references thereinGoogle Scholar
- 33.Abragam A (1961) The principles of nuclear magnetism. Oxford University Press, OxfordGoogle Scholar
- 34.Slichter CP (1990) Principles of magnetic resonance, 2nd edn. Springer, BerlinGoogle Scholar
- 40.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, 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 JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian 03, revision C.02. Gaussian Inc., Wallingford, CTGoogle Scholar
- 43.DALTON, a molecular electronic structure program, release 2.0 (2005) See http://www.kjemi.uio.no/software/dalton/dalton.html
- 45.Stanton JF, Gauss J, Watts JD et al, ACES II Mainz-Austin-Budapest version; see also Stanton JF, Gauss J, Watts JD, Lauderdale WJ, Bartlett RJ (1992) Int J Quantum Chem, Quantum Chem Symp 26:879. Current version, see http://www.aces2.de