Abstract
By doping the model complexant N3H3 with one or two lithium atoms, the geometrical and electronic structures as well as static electric properties of the resulting Li(N3H3), (N3H3)Li’ and Li(N3H3)Li’ complexes can be explored using the B3LYP, BHandHLYP, CAM-B3LYP and MP2 methods. All three complexes, especially Li(N3H3), were found to have large first hyperpolarizabilities (β 0). Meanwhile, Li(N3H3) and Li(N3H3)Li’ exhibited electride and alkalide characteristics, respectively. The dependance of electric properties of alkalide Li(N3H3)Li’ on the alkali atoms involved and the complexant layer number were revealed by investigating the related M(N3H3)Li’ and Li(N3H3)M’ (M = Na and K), and Li(N3H3) n Li’ (n = 2, 3) systems. Note that the β 0 value of alkalide M(N3H3)M’ increased not only with the increasing atomic number of the M’− anion but also with that of the M+ cation, which differs from previously reported cases. In addition, the electric properties of the Li(N3H3)Li’ alkalide were enhanced by increasing the complexant layers. However, it was found that both the complexant–complexant and the complexant–Li’ interactions reduced with the addition of N3H3 layers, so no stable structures were found for larger Li(N3H3) n Li’ complexes.
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References
Eaton DF (1991) Nonlinear optical materials. Science 253:281–287
Cheng WD, Xiang KH, Pandey R, Pernisz UC (2000) Calculations of linear and nonlinear optical properties of H-Silsesquioxanes. J Phys Chem B 104:6737–6742
Marder SR, Torruellas WE, Blanchard-Desce M, Ricci V, Stegeman GI, Gilmour S, Brédas JL, Li J, Bublitz GU, Boxer SG (1997) Large molecular third-order optical nonlinearities in polarized carotenoids. Science 276:1233–1236
Lacroix PG, Clément R, Nakatani K, Zyss J, Ledoux I (1994) Stilbazolium-MPS3 nanocomposites with large second-order optical nonlinearity and permanent magnetization. Science 263:658–660
Ichida M, Sohda T, Nakamura A (2000) Third-order nonlinear optical properties of C60CT complexes with aromatic amines. J Phys Chem B 104:7082–7084
Geskin VM, Lambert C, Brédas J-L (2003) Origin of high second- and third-order nonlinear optical response in ammonio/borato diphenylpolyene zwitterions the remarkable role of polarized aromatic groups. J Am Chem Soc 125:15 651–15 658
Champagne B, Spassova M, Jadin J-B, Kirtman B (2002) Ab initioinvestigation of doping-enhanced electronic and vibrational second hyperpolarizability of polyacetylene chains. J Chem Phys 116:3935–3946
Bouder TL, Maury O, Bondon A, Costuas K, Amouyal E, Ledoux I, Zyss J, Bozec HL (2003) Synthesis, photophysical and nonlinear optical properties of macromolecular architectures featuring octupolar tris(bipyridine) ruthenium(II) moieties: evidence for a supramolecular self-ordering in a dentritic structure. J Am Chem Soc 125:12284–12299
Avramopoulos A, Reis H, Li J, Papadopoulos MG (2004) The dipole moment, polarizabilities, and first hyperpolarizabilities of HArF. A computational and comparative study. J Am Chem Soc 126:6179–6184
Long NJ, Williams CK (2003) Metal alkynyl δ complexes: synthesis and materials. Angew Chem Int Ed 42:2586–2617
Datta A, Terenziani F (2006) Painelli a cooperative interactions in supramolecular aggregates: linear and nonlinear responses in calix[4]arenes. Chem Phys Chem 7:2168–2174
Vance FW, Hupp JT (1999) Probing the symmetry of the nonlinear optic chromophore Ru(trans-4,4-diethylaminostyryl-2,2′-bipyridine)3 2+: insight from polarized hyper-rayleigh scattering and electroabsorption (stark) spectroscopy. J Am Chem Soc 121:4047–4053
Inerbaev TM, Belosludov RV, Mizuseki H, Takahashi M, Kawazoe Y (2006) First excited state properties and static hyperpolarizability of Ruthenium(II) ammine complexes. J Chem Theory Comput 2:1325–1334
Kishi R, Nakano M, Ohta S, Takebe A, Nate M, Takahashi H, Kubo T, Kamada K, Ohta K, Champagne B, Botek E (2007) Finite-field spin-flip configuration interaction calculation of the second hyperpolarizabilities of singlet diradical systems. J Chem Theory Comput 3:1699–1707
Liu ZB, Zhou ZJ, Li Y, Li ZR, Wang R, Li QZ, Li Y, Jia FY, Wang YF, Li ZJ, Cheng JB, Sun CC (2010) Push–pull electron effects of the complexant in a Li atom doped molecule with electride character: a new strategy to enhance the first hyperpolarizability. Phys Chem Chem Phys 12:10562–10568
Nakano M, Ohta S, Tokushima K, Kishi R, Kubo T, Kamada K, Ohta K, Champagne B, Botek E, Takahashi H (2007) Second hyperpolarizability (γ) of singlet diradical system: dependence of γ on the diradical character. Chem Phys Lett 443:95–101
Xu HL, Wang FF, Chen W, Yu GT (2011) The complexant shape effect on first(hyper)polarizability of alkalides Li+(NH2CH3)4M− (M = Li, Na, and K). Int J Quantum Chem 111:3174–3183
Garcia-Borràs M, Solà M, Luis JM, Kirtman B (2012) Electronic and vibrational nonlinear optical properties of five representative electrides. J Chem Theory Comput 8:2688–2697
Zhang CC, Xu HL, Hu YY, Sun SL, Su ZM (2011) Quantum chemical research on structures, linear and nonlinear optical properties of the Li@n-acenes salt (n = 1, 2, 3, and 4). J Phys Chem A 115:2035–2040
Hu YY, Sun SL, Zhong RL, Xu HL, Su ZM (2011) Novel trumpet-shaped conjugation bridge (carbon nanocone) for nonlinear optical materials. J Phys Chem C 115:18545–18551
Kang H, Facchetti A, Jiang H, Cariati E, Righetto S, Ugo R, Zuccaccia C, Macchioni A, Stern CL, Liu ZF, Ho ST, Brown EC, Ratner MA, Marks TJ (2007) Ultralarge hyperpolarizability twisted π-electron system electro-optic chromophores: synthesis, solid-state and solution-phase structural characteristics, electronic structures, linear and nonlinear optical properties, and computational studies. J Am Chem Soc 129:3267–3286
Xu HL, Li ZR, Wu D, Wang BQ, Li Y, Gu FL, Aoki Y (2007) Structures and large NLO responses of new electrides: Li-doped fluorocarbon chain. J Am Chem Soc 129:2967–2970
Li ZJ, Wang FF, Li ZR, Xu HL, Huang XR, Wu D, Chen W, Yu GT, Gu FL, Aoki Y (2009) Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 +TCNQ−(M = Li, Na, K). Phys Chem Chem Phys 11:402–408
Li Y, Li ZR, Wu D, Li RY, Hao XY, Sun CC (2004) An ab initio prediction of the extraordinary static first hyperpolarizability for the electron-solvated cluster (FH)2{e}(HF). J Phys Chem B 108:3145–3148
Chen W, Li ZR, Wu D, Gu FL, Hao XY, Wang BQ, Li RJ, Sun CC (2004) The static polarizability and first hyperpolarizability of the water trimeranion: ab initio study. J Chem Phys 121:10489–10494
Redko MY, Vlassa M, Jackson JE, Misiolek AW, Huang RH, Dye JL (2002) “Inverse sodium hydride”: a crystalline salt that contains H+ and Na−. J Am Chem Soc 124:5928–5929
Kim J, Ichimura AS, Huang RH, Redko M, Phillips RC, Jackson JE, Dye JL (1999) Crystalline salts of Na−and K− (alkalides) that are stable at room temperature. J Am Chem Soc 121:10666–10667
Dye JL, Wagner MJ, Overney G, Huang RH, Nagy TF, Tománek D (1996) Cavities and channels in electrides. J Am Chem Soc 118:7329–7336
Dye JL (1997) Electrides: from 1D Heisenberg chains to 2D pseudo-metals. Inorg Chem 36:3816–3826
Srdanov VI, Stucky GD, Lippmaa E, Engelhardt G (1998) Evidence for an antiferromagnetic transition in a zeolite-supported cubic lattice of F centers. Phys Rev Lett 80:2449–2452
Kuo CT, Dye JL, Pratt WP Jr (1994) Effect of laser pulses on the photoelectron emission from Na+(C222)Na−. J Phys Chem 98:13575–13582
Dawes SB, Ward DL, Rydel OF, Huang RH, Dye JL (1989) Crystal structures and properties of two sodides and an electride. Inorg Chem 28:2132–2136
Sawicka A, Skurski P, Simons J (2003) Inverse sodium hydride: a theoretical study. J Am Chem Soc 125:3954–3958
Ichimura AS, Dye JL (2002) Toward inorganic electrides. J Am Chem Soc 124:1170–1171
Dye JL (2003) Electrons as anions. Science 301:607–608
Tehan FJ, Barnett BL, Dye JL (1974) Alkali anions. Preparation and crystal structure of a compound which contains the cryptated sodium cation and the sodium anion. J Am Chem Soc 13:7203–7208
Dye JL, DeBacker MG, Nicely VA (1970) Solubilization of alkali metals in tetrahydrofuran and diethyl ether by use of a cyclic polyether. J Am Chem Soc 92:5226
Chen W, Li ZR, Li Y, Sun CC, Gu FL, Aoki Y (2006) Nonlinear optical properties of alkalides Li+(calix[4]pyrrole)M− (M = Li, Na, and K): alkali anion atomic number dependence. J Am Chem Soc 128:1072–1073
Chen W, Li ZR, Wu D, Li Y, Sun CC, Gu FL (2005) The structure and the large nonlinear optical properties of Li@calix[4]pyrrole. J Am Chem Soc 127:10977–10981
Wang FF, Li ZR, Wu D, Wang BQ, Li Y, Li ZJ (2008) Structures and considerable static first hyperpolarizabilities: new organic alkalides (M+@n 6adz)M’− (M, M’= Li, Na, K; n = 2, 3) with cation inside and anion outside of the cage complexants. J Phys Chem B 112:1090–1094
Li ZJ, Li ZR, Wang FF, Luo C, Ma F, Wu D, Wang Q, Huang XR (2009) A dependence on the petal number of the static and dynamic first hyperpolarizability for electride molecules: many-petal-shaped Li-doped cyclic polyamines. J Phys Chem A 113:2961–2966
Fan LT, Li Y, Wu D, Li ZR, Sun CC (2012) Structural characteristics and large non-linear optical responses of new alkaline earth-based alkalides. Aust J Chem 65:138–144
Jing YQ, Li ZR, Wu D, Li Y, Wang BQ, Gu FL, Aoki Y (2006) Effect of the complexant shape on the large first hyperpolarizability of alkalides Li+(NH3)4M−. ChemPhysChem 7:1759–1763
Jing YQ, Li ZR, Wu D, Li Y, Wang BQ (2006) What is the role of the complexant in the large first hyperpolarizability of sodide systems Li(NH3) n Na (n = 1–4)? J Phys Chem B 110:11725–11729
Concepcion R, Dye JL (1987) Li+(en)2 .Na−: a simple crystalline sodide. J Am Chem Soc 109:7204–7206
De Backer MG, Mkadmi EB, Sauvage FX, Lelieur JP, Wagner MJ, Concepcion R, Eglin JL, Guadagnini RA, Kim J, McMills LEH, Dye JL (1994) Lithium-ethylamine and lithium-sodium-ethylamine systems: a nonmetallic liquid electride and the lowest melting fused salt. J Am Chem Soc 116:6570–6576
Gaussian 09, Revision C.01, Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JAJr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian, Inc., Wallingford CT
GaussView, version 3.09, R. Dennington II, Keith T, Millam J, Eppinnett K, Hovell WL, Gilliland R (2003) Semichem, Inc., Shawnee Mission, KS
Redko MY, Huang RH, Jackson JE, Harrison JF, Dye JL (2003) Barium azacryptand sodide, the first alkalide with an alkaline earth cation, also contains a novel dimer, (Na2)2−. J Am Chem Soc 125:2259–2263
Champagne B, Botek E, Nakano M, Nitta T, Yamaguchi K (2005) Basis set and electron correlation effects on the polarizability and second hyperpolarizability of model open-shell pπ-conjugated systems. J Chem Phys 122:114315
Yanai T, Tew DP, Handy NC (2004) A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP). Chem Phys Lett 393:51–57
Tawada Y, Tsuneda T, Yanagisawa S (2004) A long-range-corrected time-dependent density functional theory. J Chem Phys 120:8425–8433
Kanis DR, Ratner MA, Marks TJ (1994) Design and construction of molecular assemblies with large second-order optical nonlinearities. Quantum chemical aspects. Chem Rev 94:195–242
Oudar JL, Chemla DS (1977) Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment. J Chem Phys 66:2664–2668
Sun WM, Wu D, Li Y, Liu JY, He HM, Li ZR (2015) A theoretical study on novel alkaline earth-based excess electron compounds: unique alkalides with considerable nonlinear optical responses. Phys Chem Chem Phys 17:4524–4532
Acknowledgments
This work was supported by the National Natural Science Foundation of China (Grant Nos. 21173095, 21173098, 21303066) and State Key Development Program for Basic Research of China (Grant No. 2013CB834801).
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Liang, WM., Zhao, ZX., Wu, D. et al. Theoretical study on alkali-metal doped N3H3 complexes: an in-depth understanding of the origin of electride and alkalide and their large nonlinear optical properties. J Mol Model 21, 311 (2015). https://doi.org/10.1007/s00894-015-2854-3
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DOI: https://doi.org/10.1007/s00894-015-2854-3