Generalized-active-space pair-density functional theory: an efficient method to study large, strongly correlated, conjugated systems† †Electronic supplementary information (ESI) available: Singlet–triplet energy gaps for CASSCF(4,4), CASSCF(8,8), DFP-1, DFP-3, and KS-DFT methods, numbers of CSFs with more significant figures, occupation numbers for HONO–1, HONO, LUNO and LUNO+1 for FP-1 and DFP-1, singlet–triplet energy gap (kcal mol–1) of decacene for DFP-1 partition with other geometries, singlet–triplet energy gap (kcal mol–1) of hexacene for different on-top functionals, molecular geometries, and absolute energies. See DOI: 10.1039/c6sc05036k Click here for additional data file.
نویسندگان
چکیده
Department of Chemistry, Chemical The University of Minnesota, 207 Pleasant St USA. E-mail: [email protected]; cramer@u † Electronic supplementary information gaps for CASSCF(4,4), CASSCF(8,8), D numbers of CSFs with more signica HONO 1, HONO, LUNO and LUNO+1 for gap (kcal mol ) of decacene for DF singlet–triplet energy gap (kcal mol 1 functionals, molecular geometries, a 10.1039/c6sc05036k Cite this: Chem. Sci., 2017, 8, 2741
منابع مشابه
Electronic effects on singlet-triplet energy splittings in aryl-cyclopentadienylidenes
Energy gaps, AXsar (X=E, H and G) (AX.,.,-=lia,„,,,InrX“dpka,) between single (s) and triplet (I) states werecalculated at B3LTP/6-3 I 1.HO" level of theory. Our results showed that electron donating substituents(G = -NHz, -OH. -CH), -F, -Cl and -Br) at phenyl group cause to increase and electron withdrawingsubstiluents (G -CF2. and -NO:) lead to decrease the singlet-triplet energy gaps of Ar -...
متن کاملCarbene stabilization by aryl substituents. Is bigger better?
The geometries and relative stabilities of the singlet and triplet states of phenyl- (Cs), diphenyl- (C2), 1-naphthyl- (Cs), di(1-naphthyl)- (C2), and 9-anthryl-substituted (Cs) carbenes were investigated at the B3LYP/6-311+G(d,p) + ZPVE level of density functional theory. The singlet-triplet energy separations (DeltaEST), 2.7, 2.9, 3.4, 3.7, and 5.7 kcal/mol, respectively, after including an e...
متن کاملSinglet-Triplet Energy Splitting of Divalent Five-Membered Ring NI2C2H2C (M = N,P, As and Sb)
In recent work, thermal energy gaps. AE, it °PUPS gas, Ana; Gibbs free energy gaps, AG.,, between singlet(s) and triplet 0) states of 5.12C3H2C, I m (4 N. P. As and Sb) were calculated and compared with thoseanalogues. MC2113C, (M= CIL N. P. As and Sb) at B3LYIE6-311-NG" level of theory. Our itself showedthat Gibbs free energy gaps. AG, for l uu and 1 p are less than IS and I's, respectively. I...
متن کاملA benchmark theoretical study of the electronic ground state and of the singlet-triplet split of benzene and linear acenes.
A benchmark theoretical study of the electronic ground state and of the vertical and adiabatic singlet-triplet (ST) excitation energies of benzene (n=1) and n-acenes (C(4n+2)H(2n+4)) ranging from naphthalene (n=2) to heptacene (n=7) is presented, on the ground of single- and multireference calculations based on restricted or unrestricted zero-order wave functions. High-level and large scale tre...
متن کاملElectronic effects at 2 and 7 α–position of divalent unsaturated seven membered ring R2C6H6M (M=C, Si, Ge, Sn, Pb)
Electronic effects were investigated on the singlet–triplet energy gaps of divalent unsaturated seven- membered ring R2C6H6M (M=C, Si, Ge, Sn, Pb, R= –H, -CH3, i-Pr , t-Bu) at B3LYP/6-311++G** level. All the triplet states of R2C6H6C were more stable than the related the singlet states while all the singlet states of R2C6H6M (M= Si, Ge, Sn, Pb, R= –H, -CH3, i-Pr , t-Bu) were more stable than th...
متن کامل