@article {2591,
	title = {An evaluation of exchange-correlation functionals for the calculations of the ionization energies for atoms and molecules},
	journal = {Journal of Electron Spectroscopy and Related Phenomena},
	volume = {171},
	number = {1-3},
	year = {2009},
	note = {ISI Document Delivery No.: 452BQTimes Cited: 6Cited Reference Count: 82Segala, Maximiliano Chong, Delano P.},
	month = {Apr},
	pages = {18-23},
	type = {Article},
	abstract = {In this paper, ionization energies of gas-phase atoms and molecules are calculated by energy-difference method and by approximate transition-state models with density functional theory (DFT). To determine the best functionals for ionization energies, we first study the H to Ar atoms. An approximation is used in which the electron density is first obtained from Kohn-Sham computations with an exchange-correlation potential V-xc known as statistical average of orbital potentials (SAOP), after which the energy is computed from that density with 59 different exchange-correlation energy functionals E-xc. For the 18 atoms, the best E-xc functional providing an average absolute deviation (AAD) of only 0.110 eV is one known as the Krieger-Chen-lafrate-Savin functional modified by Krieger, Chen, Iafrate, and Kurth, if one uses the spin-polarized spherical atom description. On the other hand, if one imposes the condition of integer-electrons, the best functional is the Becke 1997 functional modified by Wilson, Bradley, and Tozer, with an AAD of 0.107 eV, while several other functionals perform almost as well. For molecules, we can achieve an accuracy of AAD = 0.21 eV for valence VIPs of nonperhalo molecules with Delta E(V-xc = SAOP;PBEO) using integer-electron description. For perhalo molecules our best approach is Delta E(V-xc from either E-xc or SAOP;mPW1PW) with full symmetry to obtain an AAD = 0.24 eV. (c) 2009 Elsevier B.V. All rights reserved.},
	keywords = {ADJUSTABLE-PARAMETERS, ASYMPTOTIC-BEHAVIOR, DFT, Energy-difference method, EXCITATION-ENERGIES, GENERALIZED GRADIENT APPROXIMATION, HE(II) PHOTOELECTRON-SPECTRA, Integer-electron, Ionization energy, models, ORBITAL MODEL POTENTIALS, ORGANIC-MOLECULES, PHOTO-ELECTRON SPECTRA, Slater-type orbitals, Spin-polarized spherical atom, STATISTICAL AVERAGE, TRANSITION-STATE},
	isbn = {0368-2048},
	url = {<Go to ISI>://000266515000002},
	author = {Segala, M. and Chong, D. P.}
}
@article {2544,
	title = {Synthesis and structural studies of amido, hydrazido and imido zirconium(IV) complexes incorporating a diamido/diamine cyclam-based ligand},
	journal = {Dalton Transactions},
	number = {36},
	year = {2009},
	note = {ISI Document Delivery No.: 490IKTimes Cited: 4Cited Reference Count: 83Munha, Rui F. Veiros, Luis F. Duarte, M. Teresa Fryzuk, Michael D. Martins, Ana M.},
	pages = {7494-7508},
	type = {Article},
	abstract = {The preparation, characterisation and structural analysis of a series of zirconium(IV) complexes that incorporate the diamido/diamine macrocyclic ligand Bn(2)Cyclam (Bn(2)Cyclam = 1,8-dibenzyl-1,4,8,11-tetraazacyclotetradecane) are described. The reaction of one or two equivalents of the appropriate LiNHR reagents with [(Bn(2)Cyclam)ZrCl2] give the corresponding amido-chloride [(Bn(2)Cyclam)ZrCl(NHR)] (R = Bu-t, Ph-2,Ph-6-iPr) or bis(amido) [(Bn(2)Cyclam) Zr(NHR)(2)] (R = Pr-i, Bu-t, Ph-2,Ph-6-Me) complexes, respectively. Treatment of [(Bn(2)Cyclam)ZrCl(NH2,6- iPrPh)] with one equiv. of MgClMe gives the base-free, monomeric imido complex [(Bn(2)Cyclam)Zr(N2,6-iPrPh)]. The reaction of the tBu analog with MgClMe generates a dimeric bridging imido species [{(Bn(2)Cyclam)Zr}(2)(mu-NR)(2)], which can also be obtained by thermal decomposition of [(Bn(2)Cyclam)Zr(NHtBu)(2)] in toluene. The bis(hydrazido) complex [(Bn(2)Cyclam)Zr(NHNPh2)(2)] was obtained by reaction of [(Bn(2)Cyclam)ZrCl2] and two equiv. of LiNHNPh2. A hydrazido-chloride compound [(Bn(2)Cyclam)ZrCl(N(Ph)NBu(Ph))] was generated in a one-pot reaction between [(Bn(2)Cyclam)ZrCl2], LiBu and azobenzene. DFT calculations on [(Bn(2)Cyclam)ZrXY] complexes indicate that the coordination geometry adopted by these species is dictated by the steric bulk of the ligands X and Y, varying between six-coordinate prismatic and four-coordinate tetrahedral.},
	keywords = {ASYMMETRIC HYDROAMINATION, BASIS, BASIS-SETS, CATALYTIC HYDROAMINATION, EFFECTIVE CORE POTENTIALS, GAUSSIAN-TYPE, INTRAMOLECULAR HYDROAMINATION, MOLECULAR-ORBITAL METHODS, ORGANIC-MOLECULES, POLARIZATION FUNCTIONS, TRANSITION-METALS},
	isbn = {1477-9226},
	url = {<Go to ISI>://000269493900025},
	author = {Munha, R. F. and Veiros, L. F. and Duarte, M. T. and Fryzuk,Michael D. and Martins, A. M.}
}
@article {1572,
	title = {Synthesis, reactivity, and DFT studies of tantalum complexes incorporating diamido-N-heterocyclic carbene ligands. Facile endocyclic C-H bond activation},
	journal = {Journal of the American Chemical Society},
	volume = {128},
	number = {38},
	year = {2006},
	note = {ISI Document Delivery No.: 085OFTimes Cited: 25Cited Reference Count: 73Spencer, Liam P. Beddie, Chad Hall, Michael B. Fryzuk, Michael D.},
	month = {Sep},
	pages = {12531-12543},
	type = {Article},
	abstract = {The syntheses of tantalum derivatives with the potentially tridentate diamido-N-heterocyclic carbene (NHC) ligand are described. Aminolysis and alkane elimination reactions with the diamine-NHC ligands, (Ar)[NCN]H-2 (where (Ar)[NCN]H-2 = (ArNHCH2CH2)(2)(C3N2); Ar = Mes, p-Tol), provided complexes with a bidentate amide-amine donor configuration. Attempts to promote coordination of the remaining pendent amine donor were unsuccessful. Metathesis reactions with the dilithiated diamido-NHC ligand ((Ar)[NCN]-Li-2) and various ClxTa(NR{\textquoteright}(2))(5-x) precursors were successful and generated the desired octahedral (Ar)[NCN]TaClx(NR{\textquoteright}(2))(3-x) complexes. Attempts to prepare trialkyl tantalum complexes by this methodology resulted in the formation of an unusual metallaaziridine derivative. DFT calculations on model complexes show that the strained metallaaziridine ring forms because it allows the remaining substituents to adopt preferable bonding positions. The calculations predict that the lowest energy pathway involves a tantalum alkylidene intermediate, which undergoes C-H bond activation R to the amido to form the metallaaziridine moiety. This mechanism was confirmed by examining the distribution of deuterium atoms in an experiment between (Mes)[NCN]Li-2 and Cl2Ta(CD2Ph)(3). The single-crystal X-ray structures of (p-Tol)[NCNH]Ta(NMe2)(4) (3), (Mes)[NCNH]Ta=CHPh(CH2Ph)(2) (4), (p-Tol)[NCN]Ta(NMe2)(3) (7), (Mes)[NCCN]Ta((CH2Bu)-Bu-t)(2) (11), and (Mes)[NCCN]-TaCl((CH2Bu)-Bu-t) (14) are included.},
	keywords = {COORDINATION CHEMISTRY, CRYSTAL-STRUCTURE, EFFECTIVE CORE POTENTIALS, GAUSSIAN-TYPE BASIS, METAL-CARBON BONDS, METHODS, MOLECULAR-ORBITAL, ORGANIC-MOLECULES, SET MODEL CHEMISTRY, STABLE CARBENES, STRUCTURAL-CHARACTERIZATION},
	isbn = {0002-7863},
	url = {<Go to ISI>://000240612700055},
	author = {Spencer, L. P. and Beddie, C. and Hall, M. B. and Fryzuk,Michael D.}
}
@article {1189,
	title = {A six-bowl carceplex that entraps seven guest molecules},
	journal = {Journal of the American Chemical Society},
	volume = {127},
	number = {35},
	year = {2005},
	note = {ISI Document Delivery No.: 961BOTimes Cited: 24Cited Reference Count: 63},
	month = {Sep},
	pages = {12363-12367},
	type = {Article},
	abstract = {A six-bowl carceplex that entraps seven guest molecules, 5(.)(DMSO)(7), was synthesized and characterized. The dynamics of the host shell was studied in solution in the absence and presence of water. A multiple-molecule template was found to drive the formation of 5(.)(DMSO)(x)(.)G((7-x)) (G = DMA, DMF; x = 5-7). Higher selectivity was found for species containing greater numbers of DMSO molecules.},
	keywords = {CAPTURE, COMPLEXATION, CONTAINER COMPOUNDS, COORDINATION CAGES, DIFFUSION NMR, HEMICARCERANDS, ORGANIC-MOLECULES, RESORCINARENE CAPSULE, REVERSIBLE ENCAPSULATION, TEMPLATION},
	isbn = {0002-7863},
	url = {<Go to ISI>://000231637100064},
	author = {Makeiff, D. A. and Sherman, J. C.}
}
@article {1002,
	title = {Is HAM/3 (Hydrogenic Atoms in Molecules, Version 3) a semiempirical version of DFT (density functional theory) for ionization processes?},
	journal = {Journal of the Brazilian Chemical Society},
	volume = {15},
	number = {2},
	year = {2004},
	note = {ISI Document Delivery No.: 823IBTimes Cited: 7Cited Reference Count: 69},
	month = {Mar-Apr},
	pages = {282-291},
	type = {Article},
	abstract = {We calculated valence-electron vertical ionization potentials (VIPs) of nine small molecules, plus uracil and C2F4, by several different methods: semiempirical HAM/3 and AM1 methods, different nonempirical DFT models such as uDI(B88-P86)/cc-pVTZ and -epsilon(SAOP)/TZP, and ab initio Hartree-Fock (HF)/cc-pVTZ. HAM/3 reproduced numerical values more closely to those calculated by the nonempirical DFTs than to those obtained by HF method. Core-electron binding energies (CEBEs) of aniline, nitrobenzene and p-nitro aniline, were also calculated by HAM/3 and nonempirical DeltaFT using DE method. A nonempirical DFT model, designated as DeltaE(KS) (PW86-PW91)/TZP model, resulted accurate CEBEs ( average absolute deviation of 0.14 eV) with high efficiency. Although absolute magnitude of HAM/3 CEBEs has error as much as 3 eV, the error in the chemical shifts DeltaCEBE is much smaller at 0.55 eV. While the CEBE results do not lead to any definite answer to the question in the title, the trends in valence-electron VIPs indicate that HAM/3 does not approximate DFT with accurate exchange-correlation potentials, but seems to simulate approximate functionals such as B88-P86.},
	keywords = {ACCURATE, BASIS-SET, CEBE, DFT, ELECTRON BINDING-ENERGIES, ESCA, EXCHANGE-ENERGY, HAM-3, HAM/3, MO THEORY, ORGANIC-MOLECULES, RAY PHOTOELECTRON-SPECTROSCOPY, SPECTRA, SUBSTITUTED BENZENES, vertical ionization potential, ZETA},
	isbn = {0103-5053},
	url = {<Go to ISI>://000221603000019},
	author = {Takahata, Y. and Chong, D. P. and Segala, M.}
}
@article {1014,
	title = {Mechanisms of Staudinger reactions within density functional theory},
	journal = {J. Org. Chem.},
	volume = {69},
	number = {13},
	year = {2004},
	note = {ISI Document Delivery No.: 831IDTimes Cited: 25Cited Reference Count: 96},
	month = {Jun},
	pages = {4299-4308},
	type = {Article},
	abstract = {<p>The Staudinger reactions of substituted phosphanes and azides have been investigated by using density functional theory. Four different initial reaction mechanisms have been found. All systems studied go through a cis-transition state rather than a trans-transition state or a one-step transition state. The one-step pathway of the phosphorus atom attacking the substituted nitrogen atom is always unfavorable energetically. Depending on the substituents on the azide and the phosphane, the reaction mechanism with the lowest initial reaction barrier can be classified into three categories: (1) like the parent reaction, PH3 + N3H, the reaction goes through a cis-transition state, approaches a cis-intermediate, overcomes a PN-bond-shifting transition state, reaches a four-membered ring intermediate, dissociates N-2 by overcoming a small barrier, and results in the final products: N-2 and a phosphazene; (2) once reaching the cis-intermediate, the reaction goes through the N-2-eliminating transition state and produces the final products; (3) the reaction has a concerted initial cis-transition state, in which the phosphorus atom attacks the first and the third nitrogen atoms of the azide simultaneously and reaches an intermediate, and then the reaction goes through similar steps of the first reaction mechanism. In contrast to the previous predictions on the relative stability of the unsubstituted cis-configured phosphazide intermediate and the unsubstituted trans-configured phosphazide intermediate, the total energy of the substituted trans-configured phosphazide intermediate is close to that of the substituted cis-configured phosphazide intermediate. The preference of the initial cis-transition state reaction pathway is thoroughly discussed. The relative stability of the cis- and the trans-intermediates is explored and analyzed with the aid of molecular orbitals. The effects of substituents and solvent effects on the reaction mechanisms of the Staudinger reactions are discussed in detail.</p>},
	keywords = {AB-INITIO, GAS-PHASE, GAUSSIAN-TYPE BASIS, GOLD(I) COMPLEXES, METAL-COMPLEXES, MOLECULAR-ORBITAL METHODS, ORGANIC-MOLECULES, PHOSPHINIMIDE COMPLEXES, TRIAZADIENYL FLUORIDE, X-RAY CRYSTAL},
	isbn = {0022-3263},
	url = {<Go to ISI>://000222187200003},
	author = {Tian, W. Q. and Y. A. Wang*}
}
@article {452,
	title = {Formation of a tris-capsule and a tris-carceplex from a cyclic six-bowl assembly},
	journal = {Chemical Communications},
	number = {16},
	year = {2002},
	note = {ISI Document Delivery No.: 584WWTimes Cited: 8Cited Reference Count: 25},
	month = {Aug},
	pages = {1672-1673},
	type = {Article},
	abstract = {A macrocycle composed of six cavitands was assembled into a tris-capsule and a tris-carceplex, each of which encapsulates three guest molecules.},
	keywords = {CAVITANDS, CHEMISTRY, COMPLEXATION, COORDINATION, DIMERIC CAPSULE, HYDROGEN-BONDS, MOTION, ORGANIC-MOLECULES, REVERSIBLE MOLECULAR CAPSULES, TEMPLATION},
	isbn = {1359-7345},
	url = {<Go to ISI>://000177492600008},
	author = {Mungaroo, R. and Sherman, J. C.}
}
@article {350,
	title = {Interpretation of the Kohn-Sham orbital energies as approximate vertical ionization potentials},
	journal = {Journal of Chemical Physics},
	volume = {116},
	number = {5},
	year = {2002},
	note = {ISI Document Delivery No.: 514CGTimes Cited: 203Cited Reference Count: 81},
	month = {Feb},
	pages = {1760-1772},
	type = {Article},
	abstract = {Theoretical analysis and results of calculations are put forward to interpret the energies -epsilon(k) of the occupied Kohn-Sham (KS) orbitals as approximate but rather accurate relaxed vertical ionization potentials (VIPs) I-k. Exact relations between epsilon(k) and I-k are established with a set of linear equations for the epsilon(k), which are expressed through I-k and the matrix elements epsilon(k)(resp) of a component of the KS exchange-correlation (xc) potential v(xc), the response potential v(resp). Although -I-k will be a leading contribution to epsilon(k), other I-jnot equalk do enter through coupling terms which are determined by the overlaps between the densities of the KS orbitals as well as by overlaps between the KS and Dyson orbital densities. The orbital energies obtained with "exact" KS potentials are compared with the experimental VIPs of the molecules N-2, CO, HF, and H2O. Very good agreement between the accurate -epsilon(k) of the outer valence KS orbitals and the corresponding VIPs is established. The average difference, approaching 0.1 eV, is about an order of magnitude smaller than for HF orbital energies. The lower valence KS levels are a few eV higher than the corresponding -I-k, and the core levels some 20 eV, in agreement with the theoretically deduced upshift of the KS levels compared to -I-k by the response potential matrix elements. Calculations of 64 molecules are performed with the approximate v(xc) obtained with the statistical averaging of (model) orbitals potentials (SAOP) and the calculated epsilon(k) are compared with 406 experimental VIPs. Reasonable agreement between the SAOP -epsilon(k) and the outer valence VIPs is found with an average deviation of about 0.4 eV. (C) 2002 American Institute of Physics.},
	keywords = {ASYMPTOTIC-BEHAVIOR, DENSITY-FUNCTIONAL THEORY, DERIVATIVE DISCONTINUITIES, ELECTRON BINDING-ENERGIES, EXCHANGE-CORRELATION POTENTIALS, HE(II), LOCAL POTENTIALS, MODEL POTENTIALS, ORGANIC-MOLECULES, PHOTOELECTRON-SPECTRA, STATISTICAL AVERAGE},
	isbn = {0021-9606},
	url = {<Go to ISI>://000173418600003},
	author = {Chong, D. P. and Gritsenko, O. V. and Baerends, E. J.}
}
@article {5195,
	title = {PW86-PW91 density functional calculation of vertical ionization potentials: Some implications for present-day functionals},
	journal = {International Journal of Quantum Chemistry},
	volume = {81},
	number = {1},
	year = {2001},
	note = {ISI Document Delivery No.: 380EFTimes Cited: 14Cited Reference Count: 50},
	month = {Jan},
	pages = {34-52},
	type = {Article},
	abstract = {A total of 181 vertical ionization potentials (VIPs) of 41 molecules were calculated by density functional theory (DFT) employing the Perdew-Wang 1986 (PW86) exchange and Perdew-Wang 1991 (PW91) correlation functionals and using the aug-cc-pV5Z basis and experimental ground-state geometries. The overall average absolute deviation (AAD) from experiment was found to be 0.55 eV and only 0.31 eV for linear molecules but 0.86 eV for nonplanar molecules. A number of VIPs were in error by over 2 eV. In particular, DFT performed most poorly when ionization was from an orbital with highly varying density gradients (which arise from the orbital{\textquoteright}s shape or compactness or through its density being distributed over a number of atoms). Indications are that many or all present-day functionals suffer from the same failings. (C) 2001 John Wiley \& Sons, Inc.},
	keywords = {ACCURATE, AROMATIC MOLECULES, CORRELATED MOLECULAR CALCULATIONS, DFT, EXCHANGE-ENERGY, functionals, GAUSSIAN-BASIS SETS, HE(II) PHOTOELECTRON-SPECTRA, ionization potential, ORGANIC-MOLECULES, PHOTO-ELECTRON SPECTRA, PW86, PW91, SPECTROSCOPY, WAVE-FUNCTIONS},
	isbn = {0020-7608},
	url = {<Go to ISI>://000165685400007},
	author = {Shapley, W. A. and Chong, D. P.}
}
@article {4223,
	title = {Crystal structure and thermodynamics of reversible molecular capsules},
	journal = {Journal of the American Chemical Society},
	volume = {120},
	number = {25},
	year = {1998},
	note = {ISI Document Delivery No.: ZY238Times Cited: 60Cited Reference Count: 40},
	month = {Jul},
	pages = {6252-6260},
	type = {Article},
	abstract = {The reversible encapsulation of small molecules by two rigid hemispherical molecules is described. The "bowls" are linked by four charged hydrogen bonds. The complex is highly guest-selective. A crystal structure of one complex and a thermodynamic analysis of several complexes provide an unusually vivid description of the structure and dynamics of these complexes. The relevance of these complexes as transition state models for the formation of carceplexes is also presented.},
	keywords = {BARRIER, carceplex, ENCAPSULATION, HOST GUEST COMPLEXATION, ORGANIC-MOLECULES},
	isbn = {0002-7863},
	url = {<Go to ISI>://000074600100009},
	author = {Chapman, R. G. and Olovsson, G. and Trotter, J. and Sherman, J. C.}
}
@article {4223,
	title = {Crystal structure and thermodynamics of reversible molecular capsules},
	journal = {Journal of the American Chemical Society},
	volume = {120},
	number = {25},
	year = {1998},
	note = {ISI Document Delivery No.: ZY238Times Cited: 60Cited Reference Count: 40},
	month = {Jul},
	pages = {6252-6260},
	type = {Article},
	abstract = {The reversible encapsulation of small molecules by two rigid hemispherical molecules is described. The "bowls" are linked by four charged hydrogen bonds. The complex is highly guest-selective. A crystal structure of one complex and a thermodynamic analysis of several complexes provide an unusually vivid description of the structure and dynamics of these complexes. The relevance of these complexes as transition state models for the formation of carceplexes is also presented.},
	keywords = {BARRIER, carceplex, ENCAPSULATION, HOST GUEST COMPLEXATION, ORGANIC-MOLECULES},
	isbn = {0002-7863},
	url = {<Go to ISI>://000074600100009},
	author = {Chapman, R. G. and Olovsson, G. and Trotter, J. and Sherman, J. C.}
}
@article {4224,
	title = {Reversible molecular capsules composed of two cavitands linked via an assortment of charged-hydrogen bonds and covalent bonds},
	journal = {Journal of the American Chemical Society},
	volume = {120},
	number = {38},
	year = {1998},
	note = {ISI Document Delivery No.: 125EVTimes Cited: 42Cited Reference Count: 29},
	month = {Sep},
	pages = {9818-9826},
	type = {Article},
	abstract = {Six new cavitand bowls are reported (6, 7, 8, 9, 11, and 12), as are three bis-bowl compounds (4, 13, and 14). Eight new complexes (4.guest, 7C.guest, 8C.guest, 9C.guest, 14.guest, 15.guest, 15C.guest, and 16C.guest) that reversibly encapsulate small molecules are reported. Two or more charged-hydrogen bonds (CHBs) or covalent linkages between the bowls are required to form stable complexes. Guest exchange rates vary from milliseconds to days. Thermodynamically, these complexes display an enthalpy-entropy compensation. The relative stability of complex 3.pyrazine versus complex 3.chloroform is 170000 in nitrobenzene-d(5) at 298 It. Apparent stability constants in nitrobenzene-d(5) at 298 K yield 1.1 x 10(9) M-1 for complex 3.pyrazine. The absolute stability constant for complex 4.pyrazine in nitrobenzene-d(5) at 333 K is 3.5 x 10(6) M-1.},
	keywords = {BINDING, carceplex, CHEMISTRY, ENCAPSULATION, HEMICARCERANDS, HOST-GUEST COMPLEXATION, ORGANIC-MOLECULES, RELEASE, TEMPLATION},
	isbn = {0002-7863},
	url = {<Go to ISI>://000076225200012},
	author = {Chapman, R. G. and Sherman, J. C.}
}
