Skip to main content
SpringerLink
Log in

Electronic Structure of Open-Shell Singlet Molecules: Diradical Character Viewpoint

  • Review
  • Published:
Topics in Current Chemistry Aims and scope Submit manuscript

Abstract

This chapter theoretically explains the electronic structures of open-shell singlet systems with a wide range of open-shell (diradical) characters. The definition of diradical character and its correlation to the excitation energies, transition properties, and dipole moment differences are described based on the valence configuration interaction scheme using a two-site model with two electrons in two active orbitals. The linear and nonlinear optical properties for various polycyclic aromatic hydrocarbons with open-shell character are also discussed as a function of diradical character.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15
Fig. 16
Fig. 17
Fig. 18
Fig. 19
Fig. 20
Fig. 21
Fig. 22
Fig. 23
Fig. 24
Fig. 25
Fig. 26
Fig. 27
Fig. 28
Fig. 29
Fig. 30
Fig. 31
Fig. 32
Fig. 33
Fig. 34
Fig. 35
Fig. 36
Fig. 37
Fig. 38
Fig. 39
Fig. 40
Fig. 41
Fig. 42
Fig. 43

Similar content being viewed by others

References

  1. Bendikov M, Duong HM, Starkey K, Houk KN, Carter EA, Wudl F (2004) J Am Chem Soc 126:7416–7417 (Erratum: J Am Chem Soc 126: 10493)

    Article  CAS  Google Scholar 

  2. Bettinger HF (2010) Pure Appl Chem 82:905–915

    Article  CAS  Google Scholar 

  3. Sun Z, Ye Q, Chi C, Wu J (2012) Chem Soc Rev 41:7857–7889

    Article  CAS  Google Scholar 

  4. Nakano M, Champagne B (2015) J Phys Chem Lett 6:3236–3256

    Article  CAS  Google Scholar 

  5. Nakano M, Champagne B (2016) WIREs Comput Mol Sci 6:198–210

    Article  CAS  Google Scholar 

  6. Nakano M, Kishi R, Nitta T, Kubo T, Nakasuji K, Kamada K, Ohta K, Champagne B, Botek E, Yamaguchi K (2005) J Phys Chem A 109:885–891

    Article  CAS  Google Scholar 

  7. Nakano M, Kishi R, Ohta S, Takahashi H, Kubo T, Kamada K, Ohta K, Botek E, Champagne B (2007) Phys Rev Lett 99:033001–1–4

  8. Nakano M, Yoneda K, Kishi R, Takahashi H, Kubo T, Kamada K, Ohta K, Botek E, Champagne B (2009) J Chem Phys 131:114316–1–7

  9. Kamada K, Ohta K, Kubo T, Shimizu A, Morita Y, Nakasuji K, Kishi R, Ohta S, Furukawa S, Takahashi H, Nakano M (2007) Angew Chem Int Ed 46:3544–3546

    Article  CAS  Google Scholar 

  10. Kubo T, Shimizu A, Sakamoto M, Uruichi M, Yakushi K, Nakano M, Shiomi D, Sato K, Takui T, Morita Y, Nakasuji K (2005) Angew Chem Int Ed 44:6564–6568

    Article  CAS  Google Scholar 

  11. Lambert C (2011) Angew Chem Int Ed 50:1756–1758

    Article  CAS  Google Scholar 

  12. Sun Z, Wu J (2012) J Mater Chem 22:4151–4160

    Article  CAS  Google Scholar 

  13. Sun Z, Zeng Z, Wu J (2013) Chem-Asian J 8:2894–2904

    Article  CAS  Google Scholar 

  14. Abe M (2013) Chem Rev 113:7011–7088

    Article  CAS  Google Scholar 

  15. Sun Z, Zeng Z, Wu J (2014) Acc Chem Res 47:2582–2591

    Article  CAS  Google Scholar 

  16. Nakano M (2014) Excitation Energies and Properties of Open-Shell Singlet Molecules, Springer International Publishing

  17. Kubo T (2015) Chem Lett 44:111–122

    Article  Google Scholar 

  18. Nakano M (2017) Chem Rec 17:27–62

  19. Clar E (1972) The Aromatic Sextet. Wiley, New York

    Google Scholar 

  20. Hachmann J, Dorando JJ, Avilés M, Chan GK-L (2007) J Chem Phys 127:134309–1–9

  21. Casanova D, Head-Gordon M (2009) Phys Chem Chem Phys 11:9779–9790

    Article  CAS  Google Scholar 

  22. Hajgató B, Huzak M, Deleuze MS (2011) J Phys Chem A 115:9282–9293

    Article  Google Scholar 

  23. Plasser F, Pasalic H, Gerzabek MH, Libisch F, Reiter R, Burgdörfer J, Müller T, Shepard R, Lischka H (2013) Angew Chem Int Ed 52:2581–2584

    Article  CAS  Google Scholar 

  24. Chakraborty H, Shukla A (2013) J Phys Chem A 117:14220–14229

    Article  CAS  Google Scholar 

  25. Motomura S, Nakano M, Fukui H, Yoneda K, Kubo T, Carion R, Champagne B (2011) Phys Chem Chem Phys 13:20575–20583

    Article  CAS  Google Scholar 

  26. Fukuda K, Nagami T, Fujiyoshi J, Nakano M (2015) J Phys Chem A 119:10620–10627

    Article  CAS  Google Scholar 

  27. Hayes EF, Siu AKQ (1971) J Am Chem Soc 93:2090–2091

    Article  CAS  Google Scholar 

  28. Yamaguchi K (1975) Chem Phys Lett 33:330–335

    Article  CAS  Google Scholar 

  29. Yamaguchi K (1990) In: Carbo R, Klobukowski M (eds) Self-Consistent Field: Theory and Applications. Elsevier, Amsterdam, The Netherlands, pp 727–828

    Google Scholar 

  30. Head-Gordon M (2003) Chem Phys Lett 372:508–511

    Article  CAS  Google Scholar 

  31. Nakano M, Fukui H, Minami T, Yoneda K, Shigeta Y, Kishi R, Champagne B, Botek E, Kubo T, Ohta K, Kamada K (2011) Theoret Chem Acc 130:711–724 (erratum (2011) 130:725)

  32. Nakano M, Champagne B, Botek E, Ohta K, Kamada K, Kubo T (2010) J Chem Phys 133:154302–1–15

  33. Yamanaka S, Okumura M, Nakano M, Yamaguchi K (1994) J Mol Structure (Theochem) 310:205–218

    Google Scholar 

  34. Kitagawa Y, Saito T, Nakanishi Y, Kataoka Y, Matsui T, Kawakami T, Okumura M, Yamaguchi K (2009) J Phys Chem A 113:15041–15046

    Article  CAS  Google Scholar 

  35. Calzado CJ, Cabrero J, Malrieu JP, Caballol R (2002) J Chem Phys 116:2728–2747

    Article  CAS  Google Scholar 

  36. Minami T, Ito S, Nakano M (2013) J Phys Chem A 117:2000–2006

    Article  CAS  Google Scholar 

  37. Kishi R, Nakano M (2011) J Phys Chem A 115:3565–3575

    Article  CAS  Google Scholar 

  38. Nakano M, Champagne B (2013) J Chem Phys 138: 244306-1-13

  39. Nakano M, Fukuda K, Champagne B (2016) J Phys Chem C 120:1193–1207

    Article  CAS  Google Scholar 

  40. Special Issue on Optical Nonlinearities in Chemistry (1994) Burland D, ed. Chem Rev 94:1–278

    Article  Google Scholar 

  41. Nalwa HS, Miyata S (eds) (1997) Nonlinear Optics of Organic Molecules and Polymers. CRC Press, Boca Raton, FL

    Google Scholar 

  42. Papadopoulos MG, Sadlej AJ, Leszczynski J (eds) (2006) Nonlinear optical properties of matter—from molecules to condensed phases. Springer, Dordrecht

    Google Scholar 

  43. Nakano M, Yamaguchi K (1993) Chem Phys Lett 206:285–292

    Article  CAS  Google Scholar 

  44. Nakano M, Shigemoto I, Yamada S, Yamaguchi K (1995) J Chem Phys 103:4175–4191

    Article  CAS  Google Scholar 

  45. Fukuda K, Suzuki Y, Matsui H, Nagami T, Kitagawa Y, Champagne B, Kamada K, Yamamoto Y, Nakano M (2017) Chem Phys Chem 18:142–148

  46. Chen Z, Wannere CS, Corminboeuf C, Puchta R, Schleyer PVR (2005) Chem Rev 105:3842–3888

    Article  CAS  Google Scholar 

  47. Kertesz M, Choi CH, Yang S (2005) Chem Rev 105:3448–3481

    Article  CAS  Google Scholar 

  48. Rosenberg M, Dahlstrand C, Kilså L, Ottosson H (2014) Chem Rev 114:5379–5425

    Article  CAS  Google Scholar 

  49. Chase DT, Rose BD, McClintock SP, Zakharov LN, Haley MM (2011) Angew Chem Int Ed 50:1127–1130

    Article  CAS  Google Scholar 

  50. Shimizu A, Tobe Y (2011) Angew Chem Int Ed 50:6906–6910

    Article  CAS  Google Scholar 

  51. Fix AG, Deal PE, Vonnegut CL, Rose BD, Zakharov LN, Haley MM (2013) Org Lett 15:1362–1365

    Article  CAS  Google Scholar 

  52. Shimizu A, Kishi R, Nakano M, Shiomi D, Sato K, Takui T, Hisaki I, Miyata M, Tobe Y (2013) Angew Chem Int Ed 52:6076–6079

    Article  CAS  Google Scholar 

  53. Thomas S, Kim K (2014) Phys Chem Chem Phys 16:24592–24597

    Article  CAS  Google Scholar 

  54. Ruud L, Helgaker T, Bal KL, Jørgensen P, Jensen HJA (1993) J Chem Phys 99:3847–3859

    Article  CAS  Google Scholar 

  55. Cohen HD, Roothaan CCJ (1965) J Chem Phys 43:S34–S39

    Article  CAS  Google Scholar 

  56. Fukuda K, Nagami T, Fujiyoshi J, Nakano M (2015) J Phys Chem A 119:10620–10627

    Article  CAS  Google Scholar 

  57. Nakano M, Nitta T, Yamaguchi K, Champagne B, Botek E (2004) J Phys Chem A 108:4105–4111

    Article  CAS  Google Scholar 

  58. van Gisbergen SJA, Schipper PRT, Gritsenko OV, Baerends EJ, Snijders JG, Champagne B, Kirtman B (1999) Phys Rev Lett 83:694–697

    Article  Google Scholar 

  59. Iikura H, Tsuneda T, Yanai T, Hirao K (2001) J Chem Phys 115:3540–3543

    Article  CAS  Google Scholar 

  60. Tawada Y, Tsuneda T, Yanagisawa S, Yanai T, Hirao K (2004) J Chem Phys 120:8425–8433

    Article  CAS  Google Scholar 

  61. Song J, Hirosawa T, Tsuneda T, Hirao K (2007) J Chem Phys 126:154105–1–7

  62. Kamiya M, Sekino H, Tsuneda T, Hirao K (2005) J Chem Phys 122:234111–1–10

  63. Sekino H, Maeda Y, Kamiya M, Hirao K (2007) J Chem Phys 126:014107–1–6

  64. Peach MJG, Cohen AJ, Tozer DJ (2006) Phys Chem Chem Phys 8:4543–4549

    Article  CAS  Google Scholar 

  65. Jacquemin D, Perpète EA, Medved M, Scalmani G, Frisch MJ, Kobayashi R, Adamo C (2007) J Chem Phys 126:191108–1–4

  66. Kishi R, Bonness S, Yoneda K, Takahashi H, Nakano M, Botek E, Champagne B, Kubo T, Kamada K, Ohta K, Tsuneda T (2010) J Chem Phys 132:094107-1-11

  67. Bonness S, Fukui H, Yoneda K, Kishi R, Champagne B, Botek E, Nakano M (2010) Chem Phys Lett 493:195–199

    Article  CAS  Google Scholar 

  68. Refaely-Abramson S, Baer R, Kronik L (2011) Phys Rev B 84:075144–1–8

  69. Kishi R, Nakano M, Ohta S, Takebe A, Nate M, Takahashi H, Kubo T, Kamada K, Ohta K, Botek E, Champagne B (2007) J Chem Theory Comput 3:1699–1707

    Article  CAS  Google Scholar 

  70. Nakano M, Minami T, Fukui H, Yoneda K, Shigeta Y, Kishi R, Champagne B, Botek E (2010) Chem Phys Lett 501:140–145

    Article  CAS  Google Scholar 

  71. Takatsuka K, Fueno T, Yamaguchi K (1978) Theor Chim Acta 48:175–183

    Article  CAS  Google Scholar 

  72. Staroverov VN, Davidson ER (2000) Chem Phys Lett 330:161–168

    Article  CAS  Google Scholar 

  73. Kubo T, Shimizu A, Uruichi M, Yakushi K, Nakano M, Shiomi D, Sato K, Takui T, Morita Y, Nakasuji K (2007) Org Lett 9:81–84

    Article  CAS  Google Scholar 

  74. Nakano M, Kubo T, Kamada K, Ohta K, Kishi R, Ohta S, Nakagawa N, Takahashi H, Furukawa S, Morita Y, Nakatsuji K, Yamaguchi K (2006) Chem Phys Lett 418:142–147

    Article  CAS  Google Scholar 

  75. Ohta S, Nakano M, Kubo T, Kamada K, Ohta K, Kishi R, Nakagawa N, Champagne B, Botek E, Takebe A, Umezaki S, Nate M, Takahashi H, Furukawa S, Morita Y, Nakasuji K, Yamaguchi K (2007) J Phys Chem A 111:3633–3641

    Article  CAS  Google Scholar 

  76. Nakano M, Takebe A, Kishi R, Fukui H, Minami T, Kubota K, Takahashi H, Kubo T, Kamada K, Ohta K, Champagne B, Botek E (2008) Chem Phys Lett 454:97–104

    Article  CAS  Google Scholar 

  77. Salustro S, Maschio L, Kirtman B, Rérat M, Dovesi R (2016) J Phys Chem A 120:6756–6761

    CAS  Google Scholar 

  78. Fujita M, Wakabayashi K, Nakada K, Kusakabe K (1996) J Phys Soc Jpn 65:1920–1923

    Article  CAS  Google Scholar 

  79. Jiang DE, Dai S (2008) J Phys Chem A 112:332–335

    Article  CAS  Google Scholar 

  80. Jiang DE, Sumpter BG, Dai S, J Chem Phys 127:124703–1–5

  81. Chen Z, Jiang DE, Lu X, Bettinger HF, Dai S (2007) Schleyer PvR. Houk KN 9:5449–5452

    CAS  Google Scholar 

  82. Son YW, Cohen ML, Louie SG (2006) Phys Rev Lett 97:216803–1–4

  83. Hod O, Barone V, Peralta JE, Scuseria GE (2007) Nano Lett 7:2295–2299

    Article  CAS  Google Scholar 

  84. Hachmann J, Dorando JJ, Avilés M, Chan GKL (2007) J Chem Phys 127:134309–1–9

  85. Pisani L, Chan JA, Montanari B, Harrison NM (2007) Phys Rev B 75:064418–1–9

  86. Castro Neto AH, Guinea F, Peres HMR, Novoselov KS, Geim AK (2009) Rev Mod Phys 81:109–162

    Article  CAS  Google Scholar 

  87. Yazyev OV, Wang WL, Meng S, Kaxiras E (2008) Nano Lett 8:766–

  88. Wang WL, Meng S, Kaxiras E (2008) Nano Lett 8:241–245

    Article  CAS  Google Scholar 

  89. Ezawa M (2008) Physica E 40:1421–1423

    Article  CAS  Google Scholar 

  90. Ezawa M (2007) Phys Rev B 76: 245415–1–6

  91. Fernándz-Rossier J, Palacios JJ (2007) Phys Rev Lett 99:177204–1–4

  92. Dias JR (2008) Chem Phys Lett 467:200–203

    Article  CAS  Google Scholar 

  93. Nakano M, Nagai H, Fukui H, Yoneda K, Kishi R, Takahashi H, Shimizu A, Kubo T, Kamada K, Ohta K, Champagne B, Botek E (2008) Chem Phys Lett 467:120–125

    Article  CAS  Google Scholar 

  94. Nagai H, Nakano M, Yoneda K, Fukui H, Minami T, Bonness S, Kishi R, Takahashi H, Kubo T, Kamada K, Ohta K, Champagne B, Botek E (2009) Chem Phys Lett 477:355–359

    Article  CAS  Google Scholar 

  95. Nagai H, Nakano M, Yoneda K, Kishi R, Takahashi H, Shimizu A, Kubo T, Kamada K, Ohta K, Botek E, Chanpagne B (2010) Chem Phys Lett 489:212–218

    Article  CAS  Google Scholar 

  96. Yoneda K, Nakano M (2016) Chap 27 in Graphene Science Handbook edited by Mahmood A, Ali N, Milne WI, Ozkan CS, Mitura S, Gervasoni JL, CRC Press: pp 437–455

  97. Yoneda K, Nakano M, Kishi R, Takahashi H, Shimizu A, Kubo T, Kamada K, Ohta K, Champagne B, Botek E (2009) Chem Phys Lett 480:278–283

    Article  CAS  Google Scholar 

  98. Nakano M, Kishi R, Takebe A, Nate M, Takahashi H, Kubo T, Kamada K, Ohta K, Champagne B, Botek B (2007) Comput Lett 3:333–338

    Article  CAS  Google Scholar 

  99. Yoneda K, Nakano M, Fukui H, Minami T, Shigeta Y, Kubo T, Botek E, Champagne B (2011) ChemPhysChem 12:1697–1707

    Article  CAS  Google Scholar 

  100. Yoneda K, Nakano M, Inoue Y, Inui T, Fukuda K, Shigeta Y, Kubo T, Champagne B (2012) J Phys Chem C 116:17787–17795

    Article  CAS  Google Scholar 

  101. Konishi A, Hirao Y, Matsumoto K, Kurata H, Kishi R, Shigeta Y, Nakano M, Tokunaga K, Kamada K, Kubo T (2013) J Am Chem Soc 135:1430–1437

    Article  CAS  Google Scholar 

  102. Konishi A, Hirao Y, Kurata H, Kubo T, Nakano M, Kamada K (2014) Pure Appl Chem 86:497–505

    Article  CAS  Google Scholar 

  103. Yoneda K, Matsui H, Fukuda K, Takamuku S, Kishi R, Nakano M (2014) Chem Phys Lett 595–596:220–225

    Article  Google Scholar 

  104. Lieb EH (1989) Phys Rev Lett 62:1201–1204

    Article  CAS  Google Scholar 

  105. Ovchinnikov AA (1978) Theor Chim Acta 47:297–304

    Article  CAS  Google Scholar 

  106. Nakano M, Minami T, Yoneda K, Muhammad S, Kishi R, Shigeta Y, Kubo T, Rougier L, Champagne B, Kamada K, Ohta K (2011) J Phys Chem Lett 2:1094–1098

    Article  CAS  Google Scholar 

  107. Fukuda K, Matsushita N, Minamida Y, Matsui H, Nagami T, Takamuku S, Kitagawa K, Nakano M (2017) Chemistry Select 2:2084–2087

  108. Kamada K, Ohta K, Shimizu A, Kubo T, Kishi R, Takahashi H, Botek E, Champagne B, Nakano M (2010) J Phys Chem Lett 1:937–940

    Article  CAS  Google Scholar 

  109. Kamada K, Fuku-en SI, Minamide S, Ohta K, Kishi R, Nakano M, Matsuzaki M, Okamoto H, Higashikawa H, Inoue K, Kojima S, Yamamoto Y (2013) J Am Chem Soc 135:232–241

    Article  CAS  Google Scholar 

  110. Ishida M, Shin JY, Lim JM, Lee BS, Yoon MC, Koide T, Sessier JL, Osuka A, Kim D (2011) J Am Chem Soc 133:15533–15544

    Article  CAS  Google Scholar 

  111. Li Y, Heng WK, Lee BS, Aratani N, Zafra JL, Bao N, Lee R, Sung YM, Sun Z, Huang KW, Webster RD, Navarrete JTL, Kim D, Osuka A, Casado J, Ding J, Wu J (2012) J Am Chem Soc 134:14913–14922

    Article  CAS  Google Scholar 

  112. Zeng Z, Sung YW, Bao N, Tan D, Lee R, Zafra JL, Lee BS, Ishida M, Ding J, Navarrete JTL, Li Y, Zeng W, Kim D, Huang KW, Webster RD, Casado J, Wu J (2012) J Am Chem Soc 134:14513–14525

    Article  CAS  Google Scholar 

  113. Zeng Z, Ishida M, Zafra JL, Zhu X, Sung YM, Bao N, Webster RD, Lee BS, Li RW, Zeng W, Li Y, Chi C, Navarrete JTL, Ding J, Casado J, Kim D, Wu J (2013) J Am Chem Soc 135:6363–6371

    Article  CAS  Google Scholar 

  114. Kishida H, Hibino K, Nakamura A, Kato D, Abe J (2010) This Solid Films pp 1028–2030

  115. Quah HS, Chen W, Schreyer MK, Yang H, Wong MW, Ji W, Vittal JJ (2015) Nat Comm 6:7954–1–7

  116. Takauji K, Suizu R, Awaga K, Kishida H, Nakamura A (2014) J Phys Chem C 116:5241–5246

    Google Scholar 

  117. Minami T, Nakano M (2012) J Phys Chem Lett 3:145–150

    Article  CAS  Google Scholar 

  118. Nakano M, Ito S, Nagami T, Kitagawa Y, Kubo T (2016) J Phys Chem C 120:22803–22815

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work has been supported by JSPS KAKENHI Grant Number JP25248007 in Scientific Research (A), Grant Number JP24109002 in Scientific Research on Innovative Areas “Stimuli-Responsive Chemical Species”, Grant Number JP15H00999 in Scientific Research on Innovative Areas “π-System Figuration”, and Grant Number JP26107004 in Scientific Research on Innovative Areas “Photosynergetics”. This is also partly supported by King Khalid University through a grant RCAMS/KKU/001-16 under the Research Center for Advanced Materials Science at King Khalid University, Kingdom of Saudi Arabia.

Author information

Authors and Affiliations

  1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan

    Masayoshi Nakano

  2. Center for Spintronics Research Network (CSRN), Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan

    Masayoshi Nakano

Authors
  1. Masayoshi Nakano
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Masayoshi Nakano.

Additional information

This article is part of the Topical Collection “Physical Organic Chemistry of Quinodimethanes”; edited by Yoshito Tobe, Takashi Kubo.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nakano, M. Electronic Structure of Open-Shell Singlet Molecules: Diradical Character Viewpoint. Top Curr Chem (Z) 375, 47 (2017). https://doi.org/10.1007/s41061-017-0134-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s41061-017-0134-7

Keywords

Search

Navigation