Abstract
The valence bond (VB) method has enjoyed its prime time during the early stages in the field of quantum chemistry. After the advent of molecular orbital methods VB lost its popularity but continued to be improved and refined by a small community of scientists who appreciated its power of revealing insight into the origins of chemical reactivity. This review summarizes the developments of the VB theory in the past few decades by focusing on two major areas of research: studies of the reactivity of small chemical systems and discovering the origins of enzyme catalysis. In both cases the unique capabilities of VB that facilitated discoveries of new concepts in an elegant and seemingly effortless way are discussed. It is suggested that owing to the success of these discoveries VB methodology is once again steadily gaining momentum. It is believed that VB concepts will play a major role in the future of theoretical chemistry
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References
Heitler W, London F (1927). Z Phys 44:455
London F (1928). Z Phys 46:455
Rumer G (1932). Göttinger Nach :337
Pauling L (1939). The nature of the chemical bond. Cornell University Press, Ithaca, New York
Huckel E (1930). Z Phys 60:423
Huckel E (1931). Z Phys 72:310
Huckel E (1934). Trans Faraday Soc 30:40
Dewar MJS (1952). J Am Chem Soc 74:3341
Roothaan CCJ (1951). Rev Mod Phys 23:69
Walsh AD (1953). J Chem Soc:2260
Fukui K, Yonezawa T, Shingu H (1952). J Chem Phys 20:722
Fukui K (1982). Science 218:747
Woodward RB, Hoffmann R (1969). Angew Chem Int Ed Engl 8:781
Hoffmann R, Woodward RB (1968). Acc Chem Res 1:17
Cooper DL, Gerratt J, Raimondi M (1991). Chem Rev 91:929
Hoffmann R, Shaik S, Hiberty PC (2003). Acc Chem Res 36:750
Roberts JD (2004). Acc Chem Res 37:417
Streitwieser A (2004). Acc Chem Res 37:419
Shaik S, Hiberty PC (2003). Helv Chim Acta 86:1063
Shaik S, Hiberty PC (2004). Rev Comput Chem 20:1
Evans MG, Polanyi M (1938). Trans Faraday Soc 34:11
Truhlar DG, Wyatt RE (1977). Adv Chem Phys 36:141
Murrell JN, Carter S, Farantos SC, Huxley P, Varandas AJC (1984). Molecular potential energy functions. Wiley, New York
Coulson CA, Fischer I (1949). Phil Mag 40:386
Bobrowicz FW, Goddard WA III (1977). In: Schaefer HF III (ed). Methods of electronic structure theory, Vol 3. Plenum Press, New York, p 79
Hunt WJ, Hays PJ, Goddard WA, III (1972). J Chem Phys 57:738
Goddard WA III, Harding LB (1978). Annu Rev Phys Chem 29:363
Cooper DL, Gerratt J, Raimondi M (1988). Int Rev Phys Chem 7:59
Hiberty PC, Flament JP, Noizet E (1992). Chem Phys Lett 189:259
Carter EA, Goddard WA, III (1988). J Chem Phys 88:3132
Hiberty PC, Leforestier C (1978). J Am Chem Soc 100:2012
Bernardi F, Olivucci M, McDouall JJW, Robb MA (1988). J Chem Phys 89:6365
Bernardi F, Celani P, Olivucci M, Robb MA, Suzzi-Valli G (1995). J Am Chem Soc 117:10531
Blancafort L, Celani P, Bearpark MJ, Robb MA (2003). Theor Chem Acc 110:92
Thorsteinsson T, Cooper DL, Gerrat J, Karadakov PB, Raimondi M (1996). Theor Chim Acta (Berl). 93:343
Cooper DL, Thorsteinsson T, Gerratt J (1997). Int J Quant Chem 65:439
Hirao H, Nakano H, Nakayama K (1997). J Chem Phys 107:9966
Nakano H, Sorakubo K, Nakayama K, Hirao H (2002). In: Cooper DL (ed). Valence bond theory, Elsevier, Amsterdam, p 55
van Lenthe JH, Balint-Kurti GG (1983). J Chem Phys 78:5699
Hiberty PC, Humbel S, Byrman CP, van Lenthe JH (1994). J Chem Phys 101:5969
Matsen FA (1964). Adv Quantum Chem 1:60
McWeeny R (1988). Int J Quantum Chem XXXIV:23
Wu W, Mo Y, Zhang Q (1993). J Mol Struct (THEOCHEM). 283:227
Song L, Wu W, Mo Y, Zhang Q (2003). XMVB-0.1 – An ab initio non-orthogonal valence bond program. Xiamen University, Xiamen – China
Song LC, Mo YR, Zhang QN, Wu W (2005). J comput Chem 26:514
Verbeek J, van Lenthe JH, Pulay P (1991). Mol Phys 73:1159
Verbeek J, Langenberg JH, Byrman CP, Dijkstra F, van Lenthe JH (1998). TURTLE: an ab-initio VB/VBSCF program, (now implemented in Gamess).
Hiberty PC, Shaik S (2002). Theor Chem Acc 108:255
Shaik SS (1981). J Am Chem Soc 103:3692
Pross A, Shaik SS (1983). Acc Chem Res 16:363
Shaik SS (1989). In: Bertran J, Csizmadia GI (eds). In: New theoretical concepts for understanding organic reactions NATO ASISeries, Vol C267. Kluwer, Dordrecht, Holland
Shaik SS, Hiberty PC (1991). In: Maksic ZB (ed). Theoretical concepts for chemical bonding, Vol 4. Springer, Berlin Heidelberg New York, p 324
Shaik S, Hiberty PC (1995). Adv quantum chem 26:99
Shaik S, Shurki A (1999). Angew Chem Int Ed Engl 38:587
Hiberty PC, Danovich D, Shurki A, Shaik S (1995). J Am Chem Soc 117:7760
Shaik S, Shurki A, Danovich D, Hiberty PC (2001). Chem Rev 101:1501
Kollmar H (1979). J Am Chem Soc 101:4832
Hess BJ, Schaad L (1983). J Am Chem Soc 105:7500
Shaik SS, Hiberty PC, Lefour JM, Ohanessian G (1987). J Am Chem Soc 109:363
Glendening ED, Faust R, Streitwieser A, Vollhardt KPC, Weinhold F (1993). J Am Chem Soc 115:10952
Behrens S, Koester AM, Jug K (1994). J Org Chem 59:2546
Mo Y, Wu W, Zhang Q (1994). J Phys Chem 98:10048
Minkin VI, Glukhovtsev MN, Simkin BY (1994). Aromaticity and antiaromaticity. Wiley, New York
Streitwieser AJ (1961). Molecular orbital theory for organic chemists. Wiley, New York
Badgor GM (1969). Aromatic character and aromaticity. Cambridge University Press, Cambridge, London
Garratt JP (1986). Aromaticity. Wiley, New York
Deniz AA, Peters KS, Snyder GJ (1999). Science 286:1119
George P, Trachtman M, Bock CW, Brett AM (1976). Tetrahedron 32:1357
Haas Y, Zilberg S (1995). J Am Chem Soc 117:5387
Shaik S, Zilberg S, Haas Y (1996). Acc Chem Res 29:211
Shaik S, Shurki A, Danovich D, Hiberty PC (1996). J Am Chem Soc 18:666
Shurki A, Shaik S (1997). Angew Chem Int Ed Engl 36:2205
Warshel A, Bromberg A (1970). J Chem Phys 52:1262
Raff LM, Stivers L, Proter RN, Thompson DL, Sims LB (1970). J Chem Phys 52:3449
Warshel A, Levitt M (1976). J Mol Biol 103:227
Warshel A, Weiss RM (1980). J Am Chem Soc 102:6218
Warshel A (1991). Computer modeling of chemical reactions in enzymes and solutions. Wiley, New York
Åqvist J, Warshel A (1993). Chem Rev 93:2523
Warshel A (2003). Annu Rev Bioph Biom 32:425
Zwanzig RW (1954). J Chem Phys 22:1420
Valleau JP, Torrie GM (1977). Modern theoretical chemistry. Plenum Press, New York
Hwang J-K, Warshel A (1987). J Am Chem Soc 109:715
Hwang J-K, King G, Creighton S, Warshel A (1988). J Am Chem Soc 110:5297
King G, Warshel A (1990). J Chem Phys 93:8682
Muller RP, Warshel A (1995). J Phys Chem 99:17516
Villa J, Warshel A (2001). J Phys Chem B 105:7887
Warshel A, Parson WW (2001). Q Rev Biophys 34:563
Shurki A, Warshel A (2003). Adv Prot Chem 66:249
Warshel A (2002). Acc Chem Res 35:385
Warshel A, Russell ST (1984). Q Rev Biophys 17:283
Åqvist J, Fothergill M (1996). J Biol Chem 271:10010
Luzhkov V, Åqvist J (1998). J Am Chem Soc 120:6131
Schmitt UW, Voth GA (1998). J Phys Chem B 102:5547
Schmitt UW, Voth GA (1999). J Chem Phys 111:9361
Vuilleumier R, Borgis D (1997). J Mol Struct 436–437:555
Vuilleumier R, Borgis D (1998). Chem Phys Let 284:71
Billeter SR, Webb SP, Agarwal PK, Iordanov T, Hammes-Schiffer S (2001). J Am Chem Soc 123:11262
Hammes-Schiffer S, Billeter SR (2001). Int Rev Phys Chem 20:591
Neria E, Karplus M (1997). Chem Phys Lett 267:23
Bruice TC (2002). Acc Chem Res 35:139
Bruice TC, Lightstone FC (1999). Acc Chem Res 32:127
Hur S, Bruice TC (2003). Proc Nat Acad Sci 100:12015
Shurki A, Štrajbl M, Villa J, Warshel A (2002). J Am Chem Soc 124:4097
Marcus RA (1964). Ann Rev Phys Chem 15:155
Štrajbl M, Shurki A, Kato M, Warshel A (2003). J Am Chem Soc 125:10228
Langen R, Schweins T, Warshel A (1992). Biochemistry 31:8691
Schweins T, Geyer M, Kalbitzer HR, Wittinghofer A, Warshel A (1996). Biochemistry 35:14225
Schweins T, Warshel A (1996). Biochemistry 35:14232
Shurki A, Warshel A (2004). Proteins 55:1
Glennon TM, Villa J, Warshel A (2000). Biochemistry 39:9641
Chang Y-T, Miller WH (1990). J Phys Chem 94:5884
Chang Y-T, Minichino C, Miller WH (1992). J Chem Phys 96:4341
Grochowski P, Lesyng B, Bala P, McCammon JA (1996). Int J Quant Chem 60:1143
Ischtwan J, Collins MA (1994). J Chem Phys 100:8080
Kim Y, Corchado JC, Villá J, Xing J, Truhlar DG (2000). J Chem Phys 112:2718
Albu TV, Corchado JC, Truhlar DG (2001). J Phys Chem A 105:8465
Bernardi F, Olivucci M, Robb MA (1992). J Am Chem Soc 114:1606
Garavelli M, Ruggeri F, Ogliaro F, Bearpark MJ, Bernardi F, Olivucci M, Robb MA (2003). J Comp Chem 24:1357
Mo YR, Gao JL (2000). J Phys Chem A 104:3012
Mo YR, Gao JL (2000). J Comput Chem 21:1458
Wu W, Zhong SJ, Shaik S (1998). Chemical Physics Letters 292:7
Wu W, Shaik S (1999). Chemical Physics Letters 301:37
Wu W, Danovich D, Shurki A, Shaik S (2000). J Phys Chem A 104:8744
Wu W, Luo Y, Song LC, Shaik S (2001). Phys Chem Chem Phys 3:5459
Tomasi J, Persico M (1994). Chem Rev 94:2027
Song LC, Wu W, Zhang QN, Shaik S (2004). J Phys Chem A 108:6017
Štrajbl M, Shurki A, Warshel A (2004). Proc Nat Acad Sci 100:14834
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Affiliated with the David R. Bloom Center for Pharmacy at the Hebrew University
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Shurki, A. Valence Bond – Rebirth of the Phoenix or Relic from the Stone Age. Theor Chem Acc 116, 253–261 (2006). https://doi.org/10.1007/s00214-005-0071-3
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DOI: https://doi.org/10.1007/s00214-005-0071-3