Abstract
The electronic structure of Hg(II) ions, [Hg(L) n (H2O) m ]q (L = HO−, Cl−, HS−, S2−) has been studied. Geometries were fully optimized. The B3LYP and PBE functionals give structures in good agreement with available experimental data. Calculated stretching frequencies generally correlate well with bond lengths. The role of the water molecule(s) in the solvated Hg(II) complexes has been investigated. The solvent can act as nucleophile, as hydrogen bond acceptor or as a spectator. The trans-effect results in lengthening of the Hg–L bond length. It can be understood as a competition between ligands in trans positions for the ability to donate their electron density to the 6s AO of Hg(II). The effect of the presence of water molecules on the Hg–L bond length depends on whether or not the water molecules form a direct coordination bond with Hg(II); it will not guarantee an increase in the stability of the complexes. The interaction energy, which represents the interaction between Hg(II) and ligand L and excludes all other interactions, is nucleophilicity-dependent. The interaction energy and the strength of the ligand nucleophilicity follow the order: S2− > HS− > HO− > Cl− > H2O. The charge transfer, ΔN, is an indication for the type and strength of the interaction between ligand and Hg(II). Increasing the positive and negative value of ΔN will decrease and increase the Hg(II) total NBO charge, respectively, while decreasing the electrophilicity of Hg(II) will decrease its charge and the charge transfer, ΔN.
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Mason RP, Fitzgerald WF, Morel FMM (1994) Geochim Cosmochim Acta 58:3191
Schroeder WH, Munthe J (1998) Atmos Environ 32:809
Outridge PM, Macdonald RW, Wang F, Stern GA, Dastoor AP (2008) Environ Chem 5:89
Fitzgerald WF, Lamborg CH, Hammerschmidt CR (2007) Chem Rev 107:641
Henkel G, Krebs B (2004) Chem Rev 104:801
Schroeder WH, Anlauf KG, Barrie LA, Lu JY, Steffen A, Schneeberger DR, Berg T (1998) Nature 394:331
Lu JY, Schroeder WH, Barrie LA, Steffen A, Welch HE, Martin K, Lockhart L, Hunt RV, Boila G, Richter A (2001) Geophys Res Lett 28:3219
Steffen A, Schroeder W, Bottenheim J, Narayan J, Fuentes JD (2002) Atmos Environ 36:2653
Pearson RG (1963) J Am Chem Soc 85:3533
Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512
Sigel H, McCormic DB (1970) Acc Chem Res 3:201
Martin RB (1987) J Chem Educ 64:402
Glusker JP (1991) Adv Protein Chem 42:1
Rulisek L, Vondrasek J (1998) J Inorg Biochem 71:115
Vedani A, Huhta DW (1990) J Am Chem Soc 112:4759
Comba P, Hambley TW, Strohle M (1995) Helv Chim Acta 78:2042
Comba P (1999) Coord Chem Rev 185–6:81
Ziegler T (1991) Chem Rev 91:651
Ziegler T (1995) Can J Chem-Rev Can Chim 73:743
Veillard A (1991) Chem Rev 91:743
Cory MG, Zerner MC (1991) Chem Rev 91:813
Deeth RJ (1995) Computational modeling of transition-metal centers. In: Coordination chemistry, structure and bonding, vol 82. Springer, Berlin, pp 1–42
Chermette H (1998) Coord Chem Rev 178:699
Niu SQ, Hall MB (2000) Chem Rev 100:353
Loew GH, Harris DL (2000) Chem Rev 100:407
Siegbahn PEM, Blomberg MRA (2000) Chem Rev 100:421
Frenking G, Fröhlich N (2000) Chem Rev 100:717
Hush NS, Reimers JR (2000) Chem Rev 100:775
Filatov M, Cremer D (2004) Chem Phys Chem 5:1547
Cremer D, Kraka E, Filatov M (2008) Chem Phys Chem 9:2510
Shepler BC, Balabanov NB, Peterson KAJ (2007) Chem Phys 127:164304
Shepler BC, Wright AD, Balabanov NB, Peterson KA (2007) J Phys Chem A 111:11342
Peterson KA, Shepler BC, Singleton JM (2007) Mol Phys 105:1139
Balabanov NB, Peterson KA (2004) J Chem Phys 120:6585
Shepler BC, Balabanov NB, Peterson KA (2005) J Phys Chem A 109:10363
Balabanov NB, Shepler BC, Peterson KA (2005) J Phys Chem A 109:8765
Balabanov NB, Peterson KA (2003) J Chem Phys 119:12271
Shepler BC, Peterson KA (2003) J Phys Chem A 107:1783
Balabanov NB, Peterson KA (2003) J Phys Chem A 107:7465
Tossell JA (2006) J Phys Chem A 110:2571
Tossell JA (2003) J Phys Chem A 107:7804
Tossell JA (2001) J Phys Chem A 105:935
Tossell JA (1999) Am Miner 84:877
Tossell JA (1998) J Phys Chem A 102:3587
Wiederhold JG, Cramer CJ, Daniel K, Infante I, Bourdon B, Kretzschmar R (2010) Environ Sci Technol 44:4191. doi:10.1021/es100205t
Schauble EA (2007) Geochim Cosmochim Acta 71:2170
Frisch MJT, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery Jr., JA, 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 (2003) Gaussian 03, revision B.05; Gaussian, Inc.; Pittsburgh PA
Becke AD (1993) J Chem Phys 98:5648
Becke AD (1988) Phys Rev A 38:3098
Lee CT, Yang WT, Parr RG (1988) Phys Rev B 37:785
Vosko SH, Wilk L, Nusair M (1980) Can J Phys 58:1200
Fuentealba P, Preuss H, Stoll H, von Szentpaly L (1982) Chem Phys Lett 89:418
te Velde G, Bickelhaupt FM, Baerends EJ, Guerra CF, Van Gisbergen SJA, Snijders JG, Ziegler T (2001) J Comput Chem 22:931
van Lenthe E, Ehlers A, Baerends EJ (1999) J Chem Phys 110:8943
Ziegler T, Rauk A (1979) Inorg Chem 18:1755
Perdew JP (1986) Phys Rev B 33:8822
Baerends EJ, Ellis DE, Ros P (1973) Chem Phys 2:41
Reed AE, Curtiss LA, Weinhold F (1988) Chem Rev 88:899
Parr RG, Yang W (1989) Density functional theory of atoms and molecules. Oxford University Press, Oxford
Parr RG, Donnelly RA, Levy M, Palke WE (1978) J Chem Phys 68:3801
Malone JG (1933) J Chem Phys 1:197
Parr RG, von Szentpaly L, Liu SB (1999) J Am Chem Soc 121:1922
Ohtaki H, Radnai T (1993) Chem Rev 93:1157
Subramanian V, Seff K (1980) Acta Crystallogr Sect B-Struct Commun 36:2132
Liao MS, Zhang QE, Schwarz WHE (1995) Inorg Chem 34:5597
Schwerdtfeger P, Boyd PDW, Brienne S, McFeaters JS, Dolg M, Liao MS, Schwarz WHE (1993) Inorg Chim Acta 213:233
Kaupp M, von Schnering HG (1994) Inorg Chem 33:4179
Stromberg D, Stromberg A, Wahlgren U (1991) Water Air Soil Pollut 56:681
Braune HK, Knock SZ (1933) Phys Chem Abt B 23:163
Gregg AHH, Hampson GC, Jenkins GI, Jones PLF, Sutton LE (1937) Trans Faraday Soc 33:852
Akishin PA, Spiridonov VP (1957) Kristallografiya 2:475
Maxwell LR, Mosley VM (1940) Phys Rev 57:21
Deyanov PZ, Petrov KP, Ugarov VV, Shchedrin BM, Rambidi NG (1985) J Struct Chem 26:58
Kashiwabara K, Konaka S, Kimura M (1973) Bull Chem Soc Jpn 46:10
Soldan P, Lee EPF, Wright TG (2002) J Phys Chem A 106:8619
Wang X, Andrews L (2005) Inorg Chem 44:108
Göbbels D, Wickleder MS (2004) Acta crystallogr Sect EStruct Rep. Online 60:I40
Johansso G (1971) Acta Chem Scand 25:2799
Schwarzenbach G, Widmer M (1963) Helv Chim Acta 46:2613
Barnes HL, Romberger SN, Stembrok M (1967) Econ Geol 62:957
Jay JA, Morel FMM, Hemond HF (2000) Environ Sci Technol 34:2196
Barnes HL (1979) Solubilities of ore minerals, 2nd edn. Wiley, New York
Lennie AR, Charnock JM, Pattrick RAD (2003) Chem Geol 199:199
Scott AP, Radom L (1996) J Phys Chem 100:16502
Uehara H, Konno T. Izaki Y, Horiai K, Nakagawa K, Johns JWC (1994) Can J Phys 72:1145
Braune HE, GZ (1932) Phys Chem Abt B 19:303
Clark RJHR, DM (1973) J Chem Soc Faraday Trans 2(69):1496
Sponer HT, Rev E (1941) Mod Phys 13:75
Aylett BJ (1973) Comprehensive inorganic chemistry. Pergamon Press, Elmsford
Jaque P, Marenich AV, Cramer CJ, Truhlar DG (2007) J Phys Chem C 111:5783
Li X, Tu Y, Tian H, Agren H (2010) J Chem Phys 132
Rulisek L, Havlas Z (2000) J Am Chem Soc 122:10428
Schreckenbach G, Shamov GA (2010) Acc Chem Res 43:19
Shamov GA, Schreckenbach G (2005) J Phys Chem A 109:10961. [Correction note: Shamov GA, Schreckenbach G (2006) J Phys Chem A 110:12072]
Keutsch FN, Cruzan JD, Saykally RJ (2003) Chem Rev 103:2533
Mas EM, Bukowski R, Szalewicz K (2003) J Chem Phys 118:4386
Xantheas SS (2000) Chem Phys 258:225
Boys SF, Bernardi F (1970) Mol Phys 19:553
Hartmann M, Clark T, van Eldik R (1997) J Am Chem Soc 119:7843
Stumm W, Morgan JJ (1996) Aquatic chemistry. Chemical equilibria and rates in natural waters. Wiley-Interscience, New York
Luther GW III, Tsamakis E (1989) Mar Chem 127:165
Pearson RG (1997) Chemical hardness. WILEY-VCH, Weinheim
Ayers PW, Parr RG (2010) J Am Chem Soc 2000:122
Chattaraj PK, Perez P, Zevallos J, Toro-Labbe A (2001) J Phys Chem A 105:4272
Perez P, Toro-Labbe A, Contreras R (2001) J Am Chem Soc 123:5527
Safi B, Choho K, Geerlings P (2001) J Phys Chem A 105:591
Cox H, Stace AJ (2004) J Am Chem Soc 126:3939
Solda PL, EPF, Wright TG (2002) J Phys Chem A 106:8619
Klopmann G (1968) J Am Chem Soc 90:223
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Afaneh, A.T., Schreckenbach, G. & Wang, F. Density functional study of substituted (–SH, –S, –OH, –Cl) hydrated ions of Hg2+ . Theor Chem Acc 131, 1174 (2012). https://doi.org/10.1007/s00214-012-1174-2
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DOI: https://doi.org/10.1007/s00214-012-1174-2