Abstract
In this work we present the experimental vibrational absorption (VA), vibrational circular dichroism (VCD) and Raman spectra for (+)-trans-1(S),2(S)-dicyanocyclopropane and its dideuterio derivative, trans-1(S),2(S)-dicyano-1(S),2(S)-dideuteriocyclopropane, along with VA, VCD, Raman and Raman optical activity (ROA) spectral simulations. Here we investigate the applicability of various local and non-local exchange-correlation (XC) functionals, hybrids and meta-hybrids to reproduce the vibrational spectra of this strained ring system, which also bears two cyano groups. At the highest level of theory, B3PW91/ aug-cc-pVTZ, we also investigated the trans-, cis- and gem-dicyanocyclopropane (trans-, cis-, and gem-DCCP), cyanocyclopropane (CCP) and the parent molecule cyclopropane (CP). In doing so we have investigated the electronic effects (coupling) between the cyano groups and the cyclopropane ring. In addition to providing an interpretation of the experimentally observed vibrational spectra for these molecules, this work also provides benchmark calculations for other methods, especially semi-empirical based wave function and density functional theory (DFT) based methods, such as SCC-DFTB and PM6. For the semi-empirical DFT based methods to be used for 3-membered ring systems, one ought to document their reliability for systems which were not used in the parameterization. The small 3- and 4-membered ring systems are good test systems because they contain non-standard bonding, which may be difficult to determine accurately with the approximations used in the SCC-DFTB and other semi-empirical methods. Like molecular mechanics force fields, semi-empirical methods, based on DFT and wave function quantum mechanics (WFQM), must be benchmarked against high level ab initio and DFT calculations and experimental data. In addition to bonding, the changes in the electric dipole moment, magnetic dipole moment, electric dipole-electric dipole polarizability, electric dipole-magnetic dipole polarizability and electric dipole-electric quadrupole polarizability with respect to nuclear displacement and nuclear velocity can be determined by the VA, VCD, Raman and ROA intensities. Hence it is important that the semi-empirical based DFT and wave function methods not only be parameterized to determine energies, gradients and Hessians, but also the electric and magnetic moments and their derivatives that determine the electronic and magnetic properties of these molecules and their interactions with matter and radiation. This will allow biochemists, biophysicists, molecular biologists, and physical biologists to use experimental and theoretical VA, VCD, Raman and ROA spectroscopies to probe biophysical and biochemical function and processes at the molecular level.
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References
Jalkanen KJ (1989) Ph.D. thesis, University of Southern California, Los Angeles, CA USA
Jalkanen KJ, Stephens PJ, Amos RD and Handy NC (1987). J Am Chem Soc 109: 7193
El-Azhary AA (1990) Ph.D. thesis, Department of Chemistry, University of Illinois at Chicago (UIC), Chicago, IL, USA
El-Azhary AA, Alper JS, Lowe MA and Keiderling TA (1988). Spectrochimica Acta 44A: 1315
Heintz VJ and Keiderling TA (1981). J Am Chem Soc 103: 2395
Schrumpf G and Dunker H (1985). Spectrochim Acta 41: 841
Jalkanen KJ, Bohr HG, Suhai S (1997) In: Suhai S (eds). Proceedings of the international symposium on theoretical and computational genome research. Plenum Press, New York, Spring Street, New York, pp 255–277
Tajkhorshid E, Jalkanen KJ and Suhai S (1998). J Phys Chem B 102: 5899
Frimand K, Jalkanen KJ, Bohr HG and Suhai S (2000). Chem Phys 255: 165
Jalkanen KJ, Nieminen RM, Frimand K, Bohr J, Bohr H, Wade RC, Tajkhorshid E and Suhai S (2001). Chem Phys 265: 125
Jalkanen KJ, Degtyarenko IM, Nieminen RM, Cao X, Nafie LA, Zhu F, Barron LD (2007) Theor Chem Acc. doi:10.1007/s00214-007-0276-8
Jalkanen KJ and Suhai S (1996). Chem Phys 208: 81
Deng Z, Polavarapu PL, Ford SJ, Hecht L, Barron LD, Ewig CS and Jalkanen KJ (1996). J Phys Chem 100: 2025
Han W-G, Jalkanen KJ, Elstner M and Suhai S (1998). J Phys Chem B 102: 2587
Bohr HG, Jalkanen KJ, Frimand K, Elstner M and Suhai S (1999). Chem Phys 246: 13
Deplazes E, van Bronswijk B, Zhu F, Barron LD, Ma S, Nafie LA, Jalkanen KJ (2007) Theor Chem Acc doi:10.1007/s00214-007-0361-z
Knapp-Mohammady M, Jalkanen KJ, Nardi F, Wade RC and Suhai S (1999). Chem Phys 240: 63
Jalkanen KJ, Nieminen RM, Knapp-Mohammady M and Suhai S (2003). Int J Quantum Chem 92: 239
Bunte SW, Jensen GM, McNesby KL, Goodin DB, Chabalowski CF, Nieminen RM, Suhai S and Jalkanen KJ (2001). Chem Phys 265: 13
Jürgensen VW and Jalkanen KJ (2006). Phys Biol 3: S63
Jalkanen KJ, Jürgensen VW, Claussen A, Rahim A, Jensen GM, Wade RC, Nardi F, Jung C, Degtyarenko IM, Nieminen RM, Herrmann F, Knapp-Mohammady M, Niehaus TA, Frimand K and Suhai S (2006). Int J Quantum Chem 106: 1160
Jalkanen KJ, Jürgensen VW and Degtyarenko IM (2005). Adv Quantum Chem 50: 91
Jalkanen KJ (2003). J Phys: Condens, Matter 15: S1823
El-Azhary AA and Al-Kahtani AA (2004). J Phys Chem A 108: 9601
El-Azhary AA and Al-Kahtani AA (2005). J Phys Chem A 109: 4505
El-Azhary AA and Al-Kahtani AA (2005). J Phys Chem A 109: 8041
Al-Rusaese S, Al-Kahtani AA and El-Azhary AA (2006). J Phys Chem A 110: 8676
Jalkanen KJ, Gale JD, Lassen PR, Hemmingsen L, Rodarte A, Degtyarenko IM, Nieminen RM, Christensen SB, Knapp- Mohammady M, Suhai S (2007) Theor Chem Acc. doi:10.1007/s00214-007-390-7
Elstner M, Porezag D, Jungnickel G, Elsner J, Haugk M, Frauenheim Th, Suhai S and Seifert G (1998). Phys Rev B 58: 7260
Stewart JJP (2002). J Comp Chem 10: 209
Stewart JJP (1989). J Comp Chem 10: 209, 221
Jacquemin D, Perpete EA, Scalmani G, Frisch MA, Kobayaahi R and Adamo C (2007). J Chem Phys 126: 144105
Yamanaka S, Nakata K, Ukai T, Takada T and Yamaguchi K (2006). Int J Quantum Chem 106: 3312
Walsh TR (2005). Phys Chem Chem Phys 7: 443
Xu X and Goddard WA (2004). Proc Nat Am Soc 101: 2673
Dierksen M and Grimme S (2004). J Phys Chem A 108: 10225
Rydberg H, Dion M, Jacobson N, Schroder E, Hyldgaard P, Simak S, Langreth DC and Lundquist BI (2003). Phys Rev Lett 91: 126402
Wilson PJ, Amos RD and Handy NC (1999). Chem Phys Lett 312: 475
Snijders JG, Baerends EJ and van Gisbergen SJA (1998). J Chem Phys 109: 10644
Kootstra K, Schipper PRT, Gritsenko OV, Snijders JG, Baerends EJ and van Gisbergen SJA (1998). Phys Rev A 57: 2556
Snijders JG, Baerends EJ and van Gisbergen SJA (1996). Chem Phys Lett 259: 599
Kohn W, Meir Y and Makarov DE (1998). Phys Rev Lett 80: 4153
Tozer DJ and Handy NC (1998). J Phys Chem A 102: 3162
Becke AD (1997). J Chem Phys 107: 8554
Becke AD (1996). J Chem Phys 104: 1040
Snijders JG, Baerends EJ and Gisbergen SJA (1995). J Chem Phys 103: 9347
Lee AM and Colwell SM (1994). J Chem Phys 101: 9704
Colwell SM, Murray CW, Handy NC and Amos RD (1993). Chem Phys Lett 210: 261
Handy NC, Tozer DJ, Laming GJ, Murray CW and Amos RD (1993). Isr J Chem 33: 331
Becke AD (1993). J Chem Phys 98: 5648
Becke AD (1992). J Chem Phys 97: 9173
Becke AD (1992). J Chem Phys 96: 2155
Murray CW, Laming GJ, Handy NC and Amos RD (1992). Chem Phys Lett 199: 551
Becke AD (1988). Phys Rev A 38: 3098
Lee C, Yang W and Parr RG (1988). Phys Rev B 37: 785
Shono T, Morikawa T, Okayama R-I and Oda R (1965). Die Makromoleculare Chemie 81: 142
Oda R, Shono T, Oku A and Tako H (1963). Die Makromolekulare Chemie 67: 124
Alberts IL, Andrews JS, Colwell SM, Handy NC, Jayatilaka D, Knowles PJ, Kobayashi R, Laidig KE, Laming G, Lee AM, Maslen PE, Murray CW, Rice JE, Simandiras ED, Stone AJ, Su M-D and Tozer DJ (2001). Cambridge Analytical Derivatives Package (CADPAC), 5th edn. Cambridge University, Cambridge
Jalkanen KJ, Devlin F, Polanski T, Amos RD, Handy NC and Stephens PJ (1988). In: 43nd Symposium on molecular spectroscopy. Ohio State University, Columbus OH, USA
Jalkanen KJ, Kawiecki RW, Amos RD, Handy NC, Lazzeretti P, Zanasi R and Stephens PJ (1987). In: 42nd Symposium on molecular spectroscopy. Ohio State University, Columbus OH, USA
Blom CE and Altona C (1976). Mol Phys 31: 1377
Scott WRP, Huenenberger PH, Tironi IG, Mark AE, Billeter SR, Fennen J, Torda AE, Huber T, Krueger P and Gunsteren WF (1999). J Phys Chem 103: 3596
Brooks BR, Bruccoleri RE, Olafson BD, States DJ, Swaminathan S and Karplus M (1983). J Comp Chem 4: 187
Kale L, Skeel R, Bhandarkar M, Brunner R, Gursoy A, Krawetz N, Phillips J, Shinozaki A, Varadarajan K and Schulten K (1999). J Comp Phys 151: 283
Jorgensen WL, Madura JD and Swenson CJ (1984). J Am Chem Soc 106: 6638
Jorgensen WL and Swenson CJ (1985). J Am Chem Soc 107: 569
Jorgensen WL and Swenson CJ (1985). J Am Chem Soc 107: 1489
Cornell WD, Cieplak P, Bayly CI, Gould IR, Merz KM Jr, Fergusson DM, Spellmeyer DC, Fox T, Caldwell JW and Kollman PA (1995). J Am Chem Soc 117: 5179
Weiner SJ, Kollman PA, Nguyen DT and Case DA (1986). J Comp Chem 7: 230
Weiner SJ, Kollman PA, Case DA, Singh UC, Ghio C, Alagona G, Weiner P and Profeta S (1984). J Am Chem Soc 106: 765
Maple JR, Hwang M-J, Jalkanen KJ, Stockfisch TP and Hagler AT (1998). J Comp Chem 19: 430
Talman JD and Shadwick WF (1976). Phys Rev A 14: 36
Hirata S, Ivanov S, Grabowski I, Bartlett RJ, Burke K and Talman JD (2001). J Chem Phys 115: 1635
Heaton-Burgess T, Bulat FA and Yang W (2007). Phys Rev Lett 98: 256401
Dunning TH (1970). J Chem Phys 53: 2823
Jalkanen KJ and Stephens PJ (1991). J Phys Chem 95: 5446
Kearley GJ (1995). Nucl Instrum Methods Phys Res A 354: 53
Ordejon P, Artacho E and Soler JM (1996). Phys Rev B (Rapid Comm) 53: R10441
Soler JM, Artacho E, Gale J, Garcia A, Junquera J, Ordejon P and Sanchez-Portal D (2002). J Phys Condens Matter 14: 2745
Perdew JP, Burke K and Ernyerhoh M (1996). Phys Rev Lett 77: 3865
Elstner M, Jalkanen KJ, Knapp-Mohammadi M, Frauenheim Th and Suhai S (2001). Chem Phys 263: 203
Elstner M, Jalkanen KJ, Knapp-Mohammady M, Frauenheim Th, Suhai S (2000) Chem Phys 256
Grubmüller H (1995). Phys Rev E 52: 2893
Müller EM, Grubmúller H and Meijere A (2002). J Chem Phys 116: 897
Lange OF, Schäfer LV and Grubmüller H (2006). J Comp Chem 27: 1693
Stephens PJ, Jalkanen KJ, Amos RD, Lazzeretti P and Zanasi R (1990). J Phys Chem 94: 1811
Jalkanen KJ, Stephens PJ, Lazzeretti P and Zanasi R (1988). J Chem Phys 90: 3204
Amos RD, Jalkanen KJ and Stephens PJ (1988). J Phys Chem 92: 5571
Stevens RM, Pitzer RM and Lipscomb WN (1963). J Chem Phys 38: 550
Rohra S and Görling A (2006). Phys Rev Lett 97: 013005
Becke AD (2002). J Chem Phys 117: 6935
Lee AM and Handy NC (1999). Phys Rev A 59: 209
Buehl M, Kaupp M, Malkina OL and Malkin VG (1998). J Comp Chem 20: 91
Colwell S, Handy NC and Lee AM (1996). Phys Rev A 53: 1316
Lee AM, Handy NC and Colwell SM (1995). J Chem Phys 103: 10095
Malkin VG, Malkina OL, Eriksson LA and Salahub DR (1995). Theor Comput Chem Mod Density Funct Theory 2: 273
Malkin VG, Malkina OL, Casida ME and Salahub DR (1994). J Am Chem Soc 116: 5898
Lee AM, Colwell SM and Handy NC (1994). Chem Phys Lett 229: 225
Colwell SM and Handy NC (1994). Chem Phys Lett 217: 271
Malkin VG, Malkina OL and Salahub DR (1993). Chem Phys Lett 204: 80
Malkin VG, Malkina OL and Salahub DR (1993). Chem Phys Lett 204: 87
Vignale G and Rasolt M (1989). Phys Rev B 39: 5475
Vignale G and Rasolt M (1988). Phys Rev B 37: 10685
Vignale G and Rasolt M (1989). Phys Rev Lett 62: 115
Vignale G and Rasolt M (1987). Phys Rev Lett 59: 2360
Hehre WJ, Stewart RF and Pople JA (1969). J Chem Phys 51: 2657
Binkley JS, Pople JA and Hehre WJ (1989). J Am Chem Soc 102: 939
Hehre WJ, Ditchfield R and Pople JA (1972). J Chem Phys 56: 2257
Lowe MA, Alper JS, Kawiecki RW and Stephens PJ (1986). J Phys Chem 90: 41
Lowe MA and Alper JS (1988). J Phys Chem 92: 4035
Kawiecki RW, Devlin F, Stephens PJ, Amos RD and Handy NC (1988). Chem Phys Lett 145: 411
Kawiecki RW (1988) Ph.D. thesis, University of Southern California, Los Angeles, CA, USA
Kawiecki RW, Devlin FJ, Stephens PJ and Amos RD (1991). J Phys Chem 95: 9817
Dunning TH (1971). J Chem Phys 55: 716
Bartlett RJ, Lotrich VF and Schwiegert IV (2005). J Chem Phys 123: 062205
Bartlett RJ, Grabowski I, Hirata S and Ivanov S (2005). J Chem Phys 122: 034104
El-Azhary AA and Sutter HU (1996). J Phys Chem 100: 15056
El-Azhary AA (2003). Spectrochima Acta A 59: 2009
Bürgi HB (2000). Annu Rev Phys Chem 51: 275
Partal F, Fernandez-Gomez M, Lopez-Gonzalez JJ, Navarro A and Kearley GJ (2000). Chem Phys 261: 239
Kearley GJ, Coddens G, Fillaux F, Tomkinson J and Wegener W (1993). Chem Phys 176: 279
Kearley GJ, Tomkinson J and Penfold J (1987). Zeitschrift für Pysik B 69: 63
Kearley GJ (1986). J Chem Soc Faraday Trans 2(82): 41
Tomkinson J, Warner M and Taylor AD (1984). Mol Phys 51: 381
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Festschrift in Honor of Philip J. Stephens’ 65th Birthday.
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Jalkanen, K.J., Gale, J.D., Jalkanen, G.J. et al. trans-1,2-Dicyano-cyclopropane and other cyano-cyclopropane derivatives. Theor Chem Account 119, 211–229 (2008). https://doi.org/10.1007/s00214-007-0391-6
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DOI: https://doi.org/10.1007/s00214-007-0391-6