Novel photonic materials Manthos G. Papadopoulos Institute of Organic and Pharmaceutical Chemistry. National Hellenic Research Foundation 48 Vas. Constantinou Av. Athens 11635. We will consider a series of derivatives, which have interesting linear and nonlinear optical properties
Manthos G. Papadopoulos
Institute of Organic and Pharmaceutical Chemistry.
National Hellenic Research Foundation
48 Vas. Constantinou Av.
which have interesting
linear and nonlinear optical properties
and possible applications
in the photonic industry
E = E(0) -μαFα - (1/2)ααβFαFβ - (1/6)βαβγFαFβFγ
- (1/24)γαβγδFαFβFγFδ - ...
μα : Dipole moment
βαβγ: First hyperpolarizability
(optical processing of information,
Definition of the project:
We consider insertion of a noble gas atom, Ng,
in the chemical bond A-B, leading to A-Ng-B.
Specific examples we will consider involve insertion of:
Arin HFleading toHArF
Xe in HCnH leading to HXeCnH
Xe in AuF lading to AuXeF
Which is the expanation?
A. Avramopoulos, H. Reis, J. Li and M. G. Papadopoulos, J. Am. Chem. Soc., 126, 6179 (2004).
[first covalent neutral cond. argon der.]
photolysis of HF in solid argon matrix
Point of interest:
The effect of Ar on the NLO
properties of the resulting derivative
a. L. Khriachtchev et al., Nature, 406, 874 (2000)
The dipole moment, polarizability and
first hyperpolarizability of HArF (in a.u.)
μ significant?gg: ground state dipole moment
μee: excited state dipole moment
μge: transition dipole moment
Εge: transition energy
μgg: 3.473/0.745 a.u.
μee: -0.814/-0.907 a.u.
Εge: 0.276/0.570 a.u.
Method: HF/Pol, CIS/Pol
All the above properties contribute so that
βzzz of HArF is much larger than that of HF
Reliabity of TSM significant?
HArF βzzz=-561.5 a.u. HF/Pol
-340.7 a.u. TSM
HF βzzz=-7.4 a.u. HF/Pol
-5.7 a.u. TSM
HF…Ar van der Waals complex significant?
μz=0.983 a.u. (3.473 a.u.)
αzz=19.11 a.u. (34.25 a.u.)
βzzz= -35.09 a.u. (-561.5 a.u.) ratio=16
Charge of Ar: 0.02 (0.56) ratio=28
Comparison of significant?HArF with
Αzz = 44.74 a.u. (34.25 a.u.)
βzzz = 797.5 a.u. ( -561.5 a.u.)
The linear and nonlinear optical significant?
properties of derivatives with inserted
[Proc. Chem. Soc., 218(1962)]
H significant?XeF, AuXeF, XeAuF
F. Holka,A. Avramopoulos, O. Loboda, V. Kellö, M. G. Papadopoulos,
Chem. Phys. Letters, 472, 185 (2009)
HXeF, AuXeF: not synthesized yet
XeAuF: several NgMF have been synthesized
Ng: Ar, Kr, Xe
M: Cu, Ag, Au
X: F, Cl, Br
Xe - Au bond: covalent 
Au - Xe [AuXeF] bond: partially covalent
(AXe)+ F-: significant charge transfer
A= H, Au
The barrier height
AuXeF: 119 kJmol-1
the global minimum (AuF+Xe)
from the local minimum
1. S. A. Cook and M. C. L. Gerry, J. Am Chem. Soc.126, 17000 (2004).
NBO charges significant?
L&NLO properties significant?
Basis set: aug-cc-pVQZ
ECP: Au(60), Xe(28)
The position of Xe has a great effect on αzz and βzzz
Basis set: aug-cc-pVQZ
Xe may greatly affect βzzz
Relativistic contribution: significant?
Methods: CCSD(T), Douglas-Kroll
Basis sets: PolX, PolX_DK
βzzz = great effect of relativistic contribution
Novel compounds derived by significant?
Xe inserted into HC2H and HC4H:
A.Avramopoulos, L. Serrano-Andres, J. Li, H. Reis and M. G. Papadopoulos,
J. Chem. Phys., 127, 214 (2007).
HXeC2H and HXeC2XeH:
They are prepared in a low-temperature Xe matrix using UV
photolysis of C2H2 and subsequently annealing at 40-45K
[JACS, 125, 4696 (2003)]
Tanskanen et al. reported its preparation
[JACS, 125, 16361 (2003)]
Ansbacher et al. predicted that the diacetylide Xe exists
as a metastable chemically-bound compound
[PCCP, 8, 4175 (2006)]
Resonance structures of HXeC significant?2H
Structures Weight (%)a
H–Xe+C–CH (I) 44
H·Xe·CCH (II) 26
H–Xe+–CCH (III) 14
H–Xe2+C–CH (IV) 11
H+XeC–CH (V) 5
NBO Charge Distribution significant?
(b) 8 Xe atoms arranged in a cube significant?
NBO analysis: significant?
insignificant CT takes place from the Xe environment to HXeC2H:
0.02e in the first model and
0.002e in the second model
The effect of Xe
The effect of
1 and 2
The effect of Xe significant?
in connection with effect
of the chain length
Δγzzzz = 30 000 au (approx.)
Δγzzzz = 340 000 au (approx.)
Decomposition channels of HXeC significant?2H
H+ Xe + C2H
Xe + HC2H
The barrier to this exothermic reaction is very high, 64.6 kcalmol-1
and prevents the molecule from dissociation
T. Ansbacher et al., PCCP, 8, 4175 (2006)
Vibrational properties significant?
αpvzz = [μ2](0,0)=60.13 a.u
H-Xe: 1681cm-1 [μ2](0,0)=13.1 a.u
Xe-C: 313 cm-1 [μ2](0,0)=46.8 a.u
The other modes have a negligible contribution (0.23 a.u.)
β significant?pvzzz = [μα](0,0) = -835 a.u.
H-Xe: 1681cm-1 [μα](0,0)=1212 a.u
Xe-C: 313 cm-1 [μα](0,0)=-2079a.u
The other modes have a very small contribution (32 a.u.)
Local field expression: significant?
N is the number of molecules in the cell
Vcell is the volume of the cell
ε0is the permitivity of vacuum
α,β,γ are the Cartesian components
Fk’α is the permanent local field effect on molecule k’ due to the surrounding molecules
μk’βis the dipole moment of the free molecule k’
αk’αβis the polarizability of the free moleculek’
L(11) is the Lorentz-factor tensor
Cubic closed packed with dimensions a=b=c=24.8092 Å
It involves 255 Xe atoms
Employed data significant?:
HXeC2H: Dipole moment and polarizability of at the CCSD(T) level and
Xe: experimental polarizability value (27.10 au)
Local field: Fz=-4.4x10-3 au
Changes of properties
Interpretation of the results significant?
Insertion of Xe in HCnH leads to a large increase of γzzzz
γzzzz(HXeC2H)=38740 au γzzzz(HC2H)=3380 au
(a) Excited states of lower energy
(b) An electronic spectrum which is more dense in low lying states
(c) Many non-zero contributions to the transition dipole moment matrix
The SOS model significant?
SOS computed properties significant?
αzz = 11.07 au αzz = 26.51 au
γzzzz = 3473au γzzzz = 9102 au
The SOS model reflects the expected trend
On the electronic structure of significant?H-Ng-Ng-F
(Ng=Ar, Kr, Xe) and the L&NLO properties
A.Avramopoulos, L. Serrano-Andre, J.Li, M. G. Papadopoulos,
J. Chem. Theory Comput. 6, 3365 (2010).
The diradical character of HNg2F
and the L&NLO properties
CASVB, MS-CASPT2, CCSD(T)
Electronic ground state description significant?
HArArF: 38%σ2 + 56%σσ*
HΚrΚrF: 53%σ2 + 39%σσ*
HΧeXeF: 58%σ2 + 35%σσ*
Increase of the closed shell character:
Xe > Kr > Ar
CASVB computations show: significant?
The total weight of the resonance structures
with diradical character is approx.:
99% for HArArF
97% for HKrKrF
87% for HXeXeF
The singlet-triplet ( significant?3Σ+) gap (STG)
provides an indication for the diradical
character of the system:
HAr2F 4.7 kcal/mol
HKr2F 14.7 kcal/mol
HXe2F 28.7 kcal/mol)
Wirz suggested that a significant?diradical is a molecule with
STG which does not differ by much more than
The expression “diradicaloid”
would then extend this range to ≈24 kcal/mol.
So, all the HNg2F are diradicaloids.
Method: CCSD(T)/aug-cc-pVDZ significant?
Stability significant?, Electronic Structure
and L&NLO Properties of
HXeOXeF and FXeOXeF
A.Avramopoulos, J. Li, G. Frenking, M. G. Papadopoulos,
J. Phys. Chem. A, 115, 10226 (2011)
from introduction of 2 Xe atoms
in HOF (FOF)
HXeOXeF and FXeOXeF
can be synthesized, because they are
protected by high energy barriers
VB orbitals of HXeOXeF significant?
Description of the ground state significant?
HXeXeF 58.0% σ2 + 35% σσ*
HXeΟXeH77.0% σ2 + 9% σσ*
FXeΟXeF76.5% σ2 + 10% σσ*
Insertion of O increases
the closed character
E significant?1 = 14.9
E2 = 25.5
E3 = 90.3
Dissociation paths of HXeOXeF calculated at
the CASPT2/ANO level.
Method: CASPT2/ANO significant?
ZPE has been taken into account
Reactants and products were connected through
Intrinsic Reaction Coordinate (IRC) calculations
E4 = 50.1 kcal/mol
E5 = 31.9 kcal/mol
E6 = 20.1 kcal/mol
HOXeF is another novel derivative
HXeOXeF is a significant?local minimum and is higher in energy
than several of its dissociation products:
E(HXeOXeF) – E(HOF + 2Xe) = 125.4 kcal/mol
E(HXeOXeF) – E(HO + F + 2Xe) = 85.2 kcal/mol
E(HXeOXeF) – E(OF + H + 2Xe) = 9.0 kcal/mol
E significant?1= 49.5 kcal/mol
E2= 40.5 kcal/mol
E3= 32.1 kcal/mol
Dissociation paths of FXeOXeFcalculated at
the CASPT2/ANO level
E significant?4 = 30.1 kcal/mol
E5 = 13.2 kcal/mol
E6 = 11.1 kcal/mol
Frenking et al.  found that significant?HArArF and HKrKrF
are associated with low-energy barriers.
Thus, they can NOT be observed.
HXeXeF 13.1 kcal/mol
HXeOXeF 14.9 kcal/mol
FXeOXeF 40.5 kcal/mol
Thus O and F increase the barrier
FArOArF and FKrOKrF
may be observed.
G. Frenking et al., Angew. Chem. Int. Edition,
48, 366 (2009).
L&NLO Properties significant?
Insertion of O reduces the L&NLO properties
The L&NLO properties of some significant?
Luis Serrano-Andrés, A. Avramopoulos, J. Li, P. Labéquerie, D. Begué,
V. Kellö, M. G. Papadopoulos, J. Chem Phys., 131, 134312 (2009).
Points of interest: significant?
11Ag ( diradicaloid)a
… (π2)2(π3)0 - (π2)0(π3)2
… (π2)1 (π3)1
. 14 states
31B3u (σSNi ππ *π *)
… (σSNi)1 (π 1)1 (π 2)2 (π 3)2
… (π 2)1 (π 3)1
Excited states structure of Ni(S2C2H2)2
a 11Ag [71% (p2)2(p3)0−21% (p2)0(p3)2].
b The energy difference is within the method accuracy. For simplicity the 11Ag state will be considered the ground state at this level.
c 11B1u state 65% [(π 2)1(π 3)1].
d13B1u state 92% [(π 2)1(π 3)1].
Basis set: ANO-RCC
The main findings of the CASSCF/CASPT2 computations are:
The quasidegenaracy of 11Ag and 11B1u and the large number of low lying excited states.
These features are very likely to lead to large NLO properties
Table 4. significant?A Basis set study of NiBDTa. The UBHandBHLYP functional was employed. All values are in au.
Properties of Ni(S2C2H2)2
a The B3LYP/SDD optimized geometry was employed to all calculations.
aThe properties were computed numerically. Base field: 0.005 au.
bm: Number of active electrons; a1b1b2a2: Number of orbitals
in subspaces of C2v symmetry.
Basis set: ZPolX
Method: UBHandHLYP/ significant?
has been interpreted in terms of the
quasidegeneracy of the 11Ag and 11B1u states.
As well as the many low lying excited states.
very big NLO properties.
The L&NLO properties of fullerene significant?
O. Loboda, R. Zalesny, A. Avramopoulos, J. –M. Luis, B. Kirtman, N. Tagmatarchis, H. Reis and M. G. Papadopoulos, J. Phys. Chem. A, 113, 1159 (2009).
Comment: The substituents were selected according to increasing
Hammett σp constant, which may be used as a measure
of their electron donating capabilities.
Methods: BLYP and HF(it does not have the overshoot problem).
Remark:The ratio of the BLYP and the HF values increases monotonically and becomes
quite large for the strongest donors.
Concluding remarks significant?
Colleagues who contributed to this work:
Dr Aggelos Avramopoulos, NHRF, Greece
Dr Heribert Reis, NHRF, Greece
Dr Luis Serrano Andrés, Universitat de València, Spain
Dr Jiabo Li, SciNet Technologies, USA
Dr Robert Zalesny, NHRF, Greece
Dr Oleksandr Loboda, NHRF, Greece
Professor B. Kirtman, University of California, USA
Dr Josep Maria Luis, University of Girona, Spain
Dr Nikos Tagmatarchis, NHRF, Greece
Professor Vladimir Kellö, Comenius University, Slovakia