Chemical Physics 376 (2010) 46–55

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Chemical Physics
journal homepage: www.elsevier.com/locate/chemphys

Electron flux during pericyclic reactions in the tunneling limit: Quantum

simulation for cyclooctatetraene
Hans-Christian Hege a, Jörn Manz b,⇑, Falko Marquardt a,c, Beate Paulus b, Axel Schild b
a
Abteilung Visualisierung und Datenanalyse, Zuse-Institut Berlin, Takustr. 9, 14195 Berlin, Germany
b
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany
c
Institut für Mathematik, Freie Universität Berlin, Arnimallee 6, 14195 Berlin, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Pericyclic rearrangement of cyclooctatetraene proceeds from equivalent sets of two reactants to two
Received 30 June 2010 products. In the ideal limit of coherent tunneling, these reactants and products may tunnel to each other
In final form 30 July 2010 by ring inversions and by double bond shifting (DBS). We derive simple cosinusoidal or sinusoidal time
Available online 5 August 2010
evolutions of the bond-to-bond electron fluxes and yields during DBS, for the tunneling scenario. These
Dedicated to Professor Horst Köppel on the overall yields and fluxes may be decomposed into various contributions for electrons in so called pericy-
occasion of his 60th birthday. clic, other valence, and core orbitals. Pericyclic orbitals are defined as the subset of valence orbitals which
describe the changes of Lewis structures during the pericyclic reaction. The quantum dynamical results
Keywords: are compared with the traditional scheme of fluxes of electrons in pericyclic orbitals, as provided by
Electron flux arrows in Lewis structures.
Pericyclic reaction Ó 2010 Elsevier B.V. All rights reserved.
Tunneling
Cyclooctatetraene
Quantum reaction dynamics

1. Introduction pericyclic reaction in the tunneling domain will answer these

The purpose of this paper is to present first quantum dynamics
simulations for electron fluxes during pericyclic reactions from
reactants (R) to products (P) and back, in the domain of coherent
tunneling. The results shall be compared with the traditional rule
for electronic and nuclear rearrangements of neighboring bonds
which are graphically symbolized by curved arrows in Lewis struc-
tures of R, see the textbooks of organic chemistry [1–6], inorganic
chemistry [7,8], and biochemistry [9,10]. This rule allows simple
predictions and rationalizations of syntheses [11]. Previous
theoretical investigations have already focused on various related
aspects, such as the Woodward–Hoffmann rules for the conserva-
tion of orbital symmetry [12], analysis of transition structures or
intermediates [13–16], and assignments of concerted versus
sequential mechanisms [17,18]. With full respect of these achieve-
ments [1–18], several questions remain: How many electrons actu-
ally flow? In which direction do they flow? Which orbitals are
involved? Just those – we call them pericyclic orbitals – which
are related to the bond pattern differences between the Lewis
structures of R and P? Or are other valence or core electrons in-
volved as well? The present quantum dynamics simulation of a
⇑ Corresponding author. Tel.: +49 30 838 53338; fax: +49 30 838 54792.
E-mail address: jmanz@chemie.fu-berlin.de (J. Manz).
questions.
For reference, electron-wavepacket reaction dynamics in the
pericyclic proton transfer of formamide has been analyzed by
Nagashima and Takatsuka, by means of their semiclassical
Ehrenfest theory which contains single and double electronic exci-
tations, that means for energies much higher than the tunneling
domain [19], see also [20,21].
As a case study, we shall present applications to the pericyclic
rearrangement of cyclooctatetraene (COT) by tunneling. The Lewis
structures of R and P with curved arrows are shown in Fig. 1; they
may be distinguished from each other by partial deuteration (not
shown). Both R and P have two conformations denoted R1, R2
and P1, P2, respectively, with equivalent tub-shaped non-aromatic
structures of D2d symmetry, which may be interconverted by ring
inversion (RI) [14,22–32]. That means that COT has four equivalent
isomers, R1, R2, P1 and P2. Irrespective of the two conformations
R1 and R2, the traditional rule suggests to use the Lewis structure
of R with double-headed or two single-headed curved arrows
pointing from carbon–carbon double bonds C@C to one or two
neighboring single bonds CAC, respectively. For reference, each
of the double- or single-headed arrows may be assigned to trans-
fers of two or one electrons, respectively. At the same time, nuclear
motions extend or compress the previous C@C and CAC bond
lengths to those of CAC and C@C bonds, respectively, resulting in
double bond shifting (DBS), combined with RI. Three possible sets

0301-0104/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2010.07.033
 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55
Fig. 1. Lewis structures of cyclooctatetraene (COT, C8H8) for reactant (R) and
product (P); R and P may be distinguished by partial deuteration (not shown). The
curved double- or single-headed arrows symbolize transfers of two or one
electrons, respectively. The top, bottom and middle versions on the left hand side
correspond to clockwise, counter-clockwise and pincer-motion-type fluxes of
electrons during the pericyclic reaction. The simple schemes focus on the changes
of the anti-aromatic electronic structure by double bond shifting (DBS). The
corresponding pairs of tub-shaped structures R1, R2 and P1, P2 with D2d
symmetries representing R and P are shown in Fig. 2. The four shaded areas which
are arranged in the form of a Maltese cross are assigned to the four equivalent
domains of double bonds for the reactants. DBS converts them into the corre-
sponding four domains of single bonds for the products. Each domain has two
boundaries which consist of half planes that originate from the C2 symmetry axis
and contain one of the carbon nuclei. These boundaries serve as observer planes for
monitoring the electronic flux out of the four individual domains for the double
bonds. The curved arrows suggest that pericyclic rearrangement of COT is
associated with the flux of 4  2 = 8 electrons.
of arrows in Lewis structures representing DBS of cyclooctatetra-
ene COT are shown in Fig. 1 – they symbolize different clockwise,
counter-clockwise or pincer-motion-type electron fluxes which all
lead to the same net pericyclic rearrangement of COT.
The electron flux during the pericyclic reaction will be evalu-
ated using the approach of Ref. [33] with extensions; for alterna-
tive recent approaches to electron fluxes during chemical
reactions, see [19–21,34]. Collective quantum tunneling of strongly
correlated electrons in commensurate mesoscopic rings has been
investigated previously by Baldea, Köppel and Cederbaum [35],
see also Refs. [36,37]. The method [33] is based on the Born–
Oppenheimer approximation (BOA). It has been developed and
tested against rigorous non-BOA calculations, for electron fluxes
in vibrating Hþ 2 , see also Ref. [38]. The present extension of the
method is from Hþ 2 to the much larger molecule COT where quan-
tum non-BOA simulations of electronic fluxes are prohibitive, and
from coherent vibrations to tunneling. The importance of tunneling
during pericyclic reactions, even at room temperature, has been
discovered already in Ref. [26]; tunneling during pericyclic rear-
rangement of COT has been anticipated in Ref. [29], albeit without
any explicit considerations of electron fluxes. For the present pur-
pose, coherent tunneling will be represented by a time dependent
coherent nuclear wavefunction which is constructed in analogy to
the text book example of coherent tunneling in a symmetrical dou-
ble well potential [39]. Tunneling between four equivalent isomers
has been investigated previously in Ref. [40].
For reference, it is helpful to summarize some important prop-
erties of COT, which have been discovered in the pioneering inves-
tigations [14,22–32]. It has a symmetric quadruple minimum
potential energy surface (PES) V supporting the four equivalent iso-
mers R1, R2, P1 and P2, in the electronic ground state S0(11A1); the
set of nuclear coordinates (R) at the corresponding potential min-
ima will be denoted by RR1, RR2, RP1 and RP2, respectively. This is
47
illustrated schematically in Fig. 2, compare with Refs. [14,30,31].
For convenience, the value of the PES of the four minima will be
set equal to zero. The energy gap to the first excited singlet state
S1(11A2) is large (ca 386.2 kJ/mol [31]), so that the wavefunctions
describing R1, R2, P1, P2 may well be expressed by means of the
BOA. Each of the four equivalent structures, for example R1, can
be converted into all the others, e.g. into R2, P1 and P2. Specifically,
two equivalent ring inversions RIR and RIP between the reactants
R1 and R2 as well as between the products P1 and P2, may proceed
via the corresponding transition states TSRRI and TSPRI, respec-
tively. These have D4h symmetry. Likewise, DBS converts TSRRI
via the transition state TSDBS with D8h symmetry into TSPRI. The
corresponding levels of the first excited doublet of states repre-
senting tunneling by DBS have been assigned by means of transi-
tion state spectroscopy [14]. Accordingly, tunneling from R to P
is mode-selective, even for energies close to TSDBS, which is well
above the potential minima. For comparison, for energies that al-
low over-the-barrier or close-to-the barrier processes, the most
efficient paths from reactants to products may be shortcuts, which
lead, for example, from R1 to P2 via TSDBS but not necessarily via
TSRRI and TSPRI. Instead, they may lead to each other via two differ-
ent valley ridge inflections, VRIR and VRIP which are located be-
tween TSDBS and TSRRI as well as TSPRI [30,31]. Some of the
possible paths between R1, R2, P1 and P2 are shown schematically
in Fig. 2. In contrast, the present coherent tunneling between R1,
R2, P1, P2, with energies well below the barriers, will be described
by means of the lowest quartet of delocalized vibrational eigen-
states, without any explicit reference to these paths.
The theory for electron fluxes during coherent tunneling in COT
is developed in Section 2. The results and discussions, and the con-
clusions are in Sections 3 and 4, respectively.
2. Theory
2.1. Concerted electronic and nuclear dynamics during pericyclic
rearrangement of COT in the Born–Oppenheimer approximation
The wavefunction representing pericyclic rearrangement of COT
in the electronic ground state is written in BOA as
Wðq; Q ; tÞ ¼ wel ðq; Q Þwnu ðQ ; tÞ: ð1Þ
Here wel and wnu are the real time-independent electronic and the
complex time-dependent nuclear wavefunctions, respectively,
depending on the electronic spatial and spin coordinates (q) and
on the nuclear ones Q. In Dirac notation, wnu(Q, t) = hQjwnu(t)i. The
corresponding notation for the spatial coordinates is r and R,
respectively. For convenience, we shall assume that initially, at time
t = 0, the system is prepared in one of the configurations of the reac-
tants, say R1,
Wðq; Q ; t ¼ 0Þ ¼ wel ðq; Q ÞwR1 ðQ Þ; ð2Þ
where wR1 denotes the nuclear wavefunction which is localized
close to the potential minimum for the reactant say R1, i.e., close
to RR1. In the present application, the wavefunction W(q, Q, t) should
then describe coherent tunneling from R1 to all other conforma-
tions R2, P1, P2 of COT, as well as all the subsequent tunneling pro-
cesses, including revivals or partial revivals of R1. Analogous
expressions may be derived if COT is prepared in one of the other
conformations R2, P1 or P2, represented by nuclear wavefunctions
wR2(Q), wP1(Q), wP2(Q) which are localized close to the potential
minima at RR2, RP1 and RP2, respectively.
The Hamiltonian representing COT is written as
H ¼ T nu þ Hel ; ð3Þ
where Tnu accounts for the nuclear kinetic energy, and Hel is the
electronic Hamiltonian
48 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55

Fig. 2. Topology of the symmetric quadruple minimum potential energy surface (PES) of cyclooctatetraene (COT) versus three coordinates (short-hand notation: RIR, RIP,
DBS) for ring inversions of the reactants R1, R2 (RIR) and products P1, P2 (RIP), and for double bond shifting (DBS) (schematic). The four minima of the PES support those four
equivalent tub-shaped non-aromatic structures R1, R2, P1, P2 of D2d symmetry; they may be distinguished by partial deuteration (not shown). Furthermore, the PES has two
transitions states TSRRI and TSPRI of D4h symmetry between R1 and R2 and between P1 and P2, respectively. The PES also has a transition state TSDBS with D8h symmetry
between TSRRI and TSPRI, and two valley ridge inflections VRIR and VRIP, which are located between TSDBS and TSRRI as well as TSPRI, respectively. For reference, various paths
represent over- or close-to-the-barriers transitions between the structures R1, R2, P1, P2, by RIR, RIP and by DBS, compare with Refs. [14,30,31]. Coherent tunneling between
R1, R2, R3, R4, with energies well below the barriers, is described by means of the lowest quartet of delocalized vibrational tunneling states, without any explicit reference to
these paths, see text and Fig. 3.

Hel ¼ T el þ V el;el þ V el;nu þ V nu;nu ; ð4Þ Integration over all nuclear coordinates, all electronic spin coordi-
nates and all spatial electronic coordinates but one yields the time
which includes the kinetic energy of the electrons, as well as the
dependent one-electron density qel,t(r, t), where r denotes its spatial
Coulomb interactions of the electrons (Vel,el), of the electrons and
coordinates. Likewise, for a given set of nuclear coordinates Q, inte-
nuclei (Vel,nu), and of the nuclei (Vnu,nu). All other contributions to
gration of the all-electron density qel(q; Q) over all electronic spin
H are neglected, for the present purpose. As a consequence, the elec-
coordinates and all spatial coordinates but one, yields the time-
tronic (ground state, 1S0) and nuclear spin states are conserved, in
independent one-electron density qel,Q(r; Q) depending on Q. Inte-
the present model. For fixed nuclei, the electronic time-indepen-
gration over the (conserved) nuclear spins yields the corresponding
dent Schrödinger equation
one-electron density qel,R(r; R).
Hel wel ðq; Q Þ ¼ V el ðQ Þwel ðq; Q Þ; ð5Þ
2.2. Analogy of coherent tunneling in symmetric double and quadruple
yields the electronic wavefunction wel(q; Q) and its energy in the
potentials
electronic ground state, denoted as potential energy surface (PES)
Vel(Q) for the nuclear motions. The nuclear wavefunction is propa-
Before we construct the nuclear wavefunction wnu(Q, t) describ-
gated as a solution of the nuclear time dependent Schrödinger
ing coherent tunneling from R1 to all other conformations of COT,
(nuTDSE) equation,
it is helpful to recall the derivation of the tunneling wavefunction
d e [39], written with
~ nu ðQ ; tÞ in a symmetric double well potential V
w
ih w ðQ ; tÞ ¼ Hnu wnu ðQ ; tÞ; ð6Þ
dt nu tilde, for reference. By analogy, the potential minima for the reac-
tant R e and for the product Pe (possibly distinguishable by isotopic
starting from the initial wavefunction wnu (Q, t = 0) = wR1(Q). The
substitution) are located at R ~ and R e , respectively. Likewise, the
nuclear Hamiltonian is e R e P
nuclear wavefunctions representing R e and P e with the lowest pos-
Hnu ¼ T nu þ V el ðQ Þ: ð7Þ sible energy e ~ ðQ Þ and w
E are written as w ~ ðQ Þ; they are localized
eR eP
The resulting all-electron-all-nuclear density is ~ and R
close to R ~ , respectively. These localized wavefunctions
eR eP
may be expressed in terms of the doublet of the delocalized gerade
qðq; Q ; tÞ ¼ jwel ðq; Q Þj2 jwnu ðQ ; tÞj2 ¼ qel ðq; Q Þqnu ðQ ; tÞ: ð8Þ (+) and ungerade () eigenfunctions [39]
 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55 49

~ ðQ Þ ¼ p1ffiffiffi ðw
w ~ þ ðQ Þ þ w
~  ðQ ÞÞ; ð9Þ
w+(Q), w+(Q), w(Q) with eigenenergies E++, E+, E+, E,
eR 2 respectively,
~ ðQ Þ ¼ p1ffiffiffi ðw
w ~ þ ðQ Þ  w
~  ðQ ÞÞ; ð10Þ 1
eP 2 wR1 ðQ Þ ¼ ðw ðQ Þ þ wþ ðQ Þ þ wþ ðQ Þ þ w ðQ ÞÞ; ð21Þ
2 þþ
~ þ ðQ Þ and w
respectively. The w ~  ðQ Þ are obtained as eigenstates of 1
wR2 ðQ Þ ¼ ðwþþ ðQ Þ þ wþ ðQ Þ  wþ ðQ Þ  w ðQ ÞÞ; ð22Þ
the time-independent nuclear Schrödinger equation (nuTISE) 2
1
e nu w
~  ðQ Þ ¼ e ~  ðQ Þ; wP1 ðQ Þ ¼ ðwþþ ðQ Þ  wþ ðQ Þ  wþ ðQ Þ þ w ðQ ÞÞ; ð23Þ
H Ew ð11Þ 2
1
where e
E þ and e
E  are the levels of the lowest tunneling doublet. wP2 ðQ Þ ¼ ðwþþ ðQ Þ  wþ ðQ Þ þ wþ ðQ Þ  w ðQ ÞÞ: ð24Þ
2
Both wavefunctions (9), (10) have the same mean energy
  The first and second subscripts indicate gerade (+) or ungerade ()
~¼1 e
E Eþ þ e
E : ð12Þ symmetries with respect to RI and DBS, respectively. The localized
2 wavefunctions (21)–(24) and the delocalized eigenstates are illus-
The tunneling splitting is trated schematically in Fig. 3.
All wavefunctions (21)–(24) have the same mean energy,
De
E¼e
E  e
Eþ: ð13Þ
1
The solution of the nuTDSE (6), starting from the reactant wave- E¼ ðEþþ þ Eþ þ Eþ þ E Þ: ð25Þ
4
function (9), is obtained as Eq. (9) extended by time-dependent
The corresponding tunneling splittings and the relations to the tun-
coefficients
neling times are
~ ðQ ; tÞ ¼ p1ffiffiffi ðw
w ~ þ ðQ Þ expði e ~  ðQ Þ expði e
E þ t=hÞ þ w E  t=
hÞÞ: ð14Þ DEDBS ¼ Eþ  Eþþ  E  Eþ ð26Þ
eR 2
and
The resulting absolute square of the correlation function
     DEDBS sDBS ¼ h; ð27Þ
hw ~ R ðtÞi ¼ 1 exp i e
~ R ð0Þjw E þ t=h þ exp i e
E  t=h ; ð15Þ
2 for DBS as well as

yields the probability of observing the system as reactant DERI ¼ Eþ  Eþþ  E  Eþ ð28Þ
e ðtÞ ¼ jhw
P ~ ðtÞij ¼ cos2 ðD e
~ ð0Þjw 2
E pt=hÞ: ð16Þ and
e
R e e R R
DERI sRI ¼ h; ð29Þ
Likewise, the probability of observing the system as product is
for RI. We anticipate the relations
e ðtÞ ¼ jhw
P ~ ðtÞij2 ¼ sin2 ðD e
~ ð0Þjw E pt=hÞ: ð17Þ
e
P e e P R DEDBS  DERI ; ð30Þ
e ðtÞ and P
Obviously, P e ðtÞ oscillate periodically, with tunneling
eR eP or
time s
~ which is related to the tunneling splitting,
sDBS  sRI ; ð31Þ
De
Es~ ¼ h: ð18Þ
because of the different potential barriers for tunneling by DBS
The corresponding all-electron-all-nuclear density is compared to RI [28,30,31],

q~ ðq; Q ; tÞ ¼ jw~ el ðq; Q Þj2 jw~ eR ðQ ; tÞj2 ¼ q~ el ðq; Q Þq~ nu ðQ ; tÞ: ð19Þ V DBS > V RI ; ð32Þ
the most recent Ref. [31] suggests VDBS = 55.2 and VRI = 51.9 kJ/mol.
Integration of the all-electron density q ~ el ðq; Q Þ over all nuclear
The solution of the nuTDSE (6), starting from the reactant wave-
coordinates, all electronic spin coordinates and all spatial electronic
function (21), is
coordinates but one (dq ~ ) yields the one-electron density q ~ el;t ðr; tÞ.
Taking into account that the nuclear wavefunctions are centered 1
wR1 ðQ ; tÞ ¼ ðw ðQ ÞeiEþþ t=h þ wþ ðQ ÞeiEþ t=h
at Re with probability Pe ðtÞ and at Re with probability P e ðtÞ, we 2 þþ
R R P P
obtain the approximation þ wþ ðQ ÞeiEþ t=h þ w ðQ ÞeiE t=h Þ: ð33Þ
Z
q~ el;t ðr; tÞ ¼ q~ el ðq; Q Þq~ nu ðQ ; tÞdQ dq~ The resulting absolute square of the nuclear correlation function
Z h i 1
hwR1 ð0ÞjwR1 ðtÞi ¼ ðexpðiEþþ t=hÞ þ expðiEþ t=hÞ
 q~ el;R ðr; ReR Þ dðR  ReR Þ Pe eR ðtÞ þ dðR  ReP Þ PeeP ðtÞ dR 4
þ expðiEþ t=hÞ þ expðiE t=hÞÞ; ð34Þ
q e ðtÞ þ q
~ el;R ðr; Re Þ P e ðtÞ:
~ el;R ðr; ReÞ P
e
R R e P P
yields the probability of observing COT as reactant R1,
ð20Þ
PR1 ðtÞ ¼ jhwR1 ð0ÞjwR1 ðtÞij2
2.3. Nuclear tunneling dynamics of COT ¼ cos2 ðDEDBS pt=hÞ cos2 ðDERI pt=hÞ: ð35Þ
Likewise, the probabilities of observing COT as R2, P1 or P2 are
The derivation of the corresponding expressions for coherent
2
tunneling of COT is entirely analogous to Eqs. (1)–(20), except that PR2 ðtÞ ¼ jhwR2 ð0ÞjwR1 ðtÞij2 ¼ cos2 ðDEDBS pt=hÞ sin ðDERI pt=hÞ; ð36Þ
we have to consider four potential minima supporting two reac- 2 2 2
PP1 ðtÞ ¼ jhwP1 ð0ÞjwR1 ðtÞij ¼ sin ðDEDBS pt=hÞ cos ðDERI pt=hÞ; ð37Þ
tants R1, R2 and two products P1, P2 instead of just two minima
supporting fR and eP, respectively. The corresponding localized nu- and
clear wavefunctions wR1(Q), wR2(Q), wP1(Q), wP2(Q), are superposi- 2 2
tions of the lowest quartet of delocalized eigenstates w++(Q), PP2 ðtÞ ¼ jhwP2 ð0ÞjwR1 ðtÞij2 ¼ sin ðDEDBS pt=hÞ sin ðDERI pt=hÞ; ð38Þ
50 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55

Fig. 3. Topologies of the quartet of delocalized nuclear eigenstates w++(Q), w+(Q), w+(Q), w(Q) of COT, and the corresponding localized wave functions representing
reactants R1, R2 and products P1 and P2 (schematic). The bird’s eye view shows equicontours of the wavefunctions representing the eight carbon nuclei of COT. The
delocalized eigenstates have 32 lobes, which are centered at the four different positions for those eight carbon nuclei in configurations R1, R2, P1, P2. These 32 lobes are
arranged as 16 dumbbells, with front and back lobes which are shown as balls and partially hidden balls, respectively. The straight single and double lines indicate single and
double bonds of the Lewis structures of the reactants and products, respectively, to guide the eye from the delocalized wavefunctions to the localized ones. Dark and bright
lobes have positive and negative values, respectively, due to excitations of the nuclear motions for DBS (w+), ring inversion (w+), or both (w). The linear combinations
(21)–(24) imply destructive interferences which eliminate 32–8 lobes of the delocalized wavefunctions, to the benefit of constructive superpositions of eight lobes for the
localized wavefunctions WR1, WR2, WP1, WP2 representing the four different configurations R1, R2, P1, P2, respectively. The delocalized wavefunctions are arranged in
energetic order E++ < E+ < E+ < E. The corresponding set of localized wave functions have the same mean energies E, Eq. (25).

respectively. Gratifyingly,
PR1 ðtÞ þ PR2 ðtÞ þ PP1 ðtÞ þ PP2 ðtÞ ¼ 1:
The probability of finding the COT as reactant R, irrespective of the
configurations R1 or R2, is
PR ðtÞ ¼ P R1 ðtÞ þ P R2 ðtÞ ¼ cos2 ðDEDBS pt=hÞ:
Likewise,
2
PP ðtÞ ¼ PP1 ðtÞ þ PP2 ðtÞ ¼ sin ðDEDBS pt=hÞ;
for the products. Expressions (40), (41) for COT are entirely analo-
gous to (16), (17) for the model system with a symmetric double
well PES. Taking into account the relations (30), (31), comparison
of expressions (35)–(38) and (40), (41) allow illuminating interpre-
tations, e.g. slow tunneling from R to P by DBS is modulated by
more rapid tunneling between R1 and R2 as well as between P1
and P2, by means of RI. Averaging over very long times (indicated
by P) yields equal mean probabilities for observing COT in configu-
rations R1, R2, P1, P2,
1
PR1 ¼ PR2 ¼ PP1 ¼ PP2 ¼ : ð42Þ
4
bonds of the reactant (DB, R), with equal volumes V ¼ V DB;R , to four
domains of single bonds of the products (SB, P), with corresponding
ð39Þ equal volumes V ¼ V SB;P , see Fig. 1. The individual volumes have
corresponding boundaries (areas) A = ADB,R or A = ASB,P, respec-
tively. These boundaries consist of two half planes that originate
from the C2 symmetry axis such that each of them contains one
of two neighboring carbon nuclei which are connected by a
ð40Þ carbon–carbon bond. The electronic flux out of one of these
domains with volume V through its boundary A is [33]
Z
ð41Þ d
F el ðt; AÞ ¼ dV qel;t ðr; tÞ: ð43Þ
dt V
The time-dependent one-electron density qel,t(r, t) and the time-
independent one-electron density qel,R(r; R) are evaluated as de-
scribed in the text after Eq. (8). By analogy with the derivation of
expression (20) for the one-electron density q ~ el;t ðr; tÞ for tunneling
in a symmetric double well potential, we take into account that
the nuclear wavefunctions are centered at RR1, RR2, RP1 or RP2 with
probabilities PR1(t), PR2(t), PP1(t), PP2(t), respectively, cf. Eqs. (35)–
(38), thus
qel;t ðr; tÞ  qel;R ðr; RR1 ÞPR1 ðtÞ þ qel;R ðr; RR2 ÞPR2 ðtÞ
þ qel;R ðr; RP1 ÞPP1 ðtÞ þ qel;R ðr; RP2 ÞPP2 ðtÞ: ð44Þ

2.4. Electron flux during pericyclic tunneling of COT
For reference, the curved arrows in the Lewis structure of the
reactant R suggest that four double bonds of COT are converted
to four single bonds of the products P, such that altogether 4  2
electrons are transferred from four equivalent domains of double
Inserting the approximation (44) into (43) allows to express the
electronic flux (43) as the sum of two contributions which depend
on the nuclear configurations of the reactants (R) and products (P)
F el ðt; AÞ  F el;R ðt; AÞ þ F el;P ðt; AÞ: ð45Þ
Specifically, for the double bond domain V DB;R of the reactants
 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55 51

Z Z !
d the absolute value of the negative yield (53) – is just the difference
F el;DB;R ðt; AÞ ¼ PR1 ðtÞ dV qel;R ðr; RR1 Þ þ P R2 ðtÞ dV qel;R ðr; RR2 Þ
dt V DB;R V DB;R
between the number of electrons in the four equivalent domains of
the double bonds of the reactants, with equal volumes V DB;R , minus
d 
 PR1 ðtÞN el;DB;R ðR1Þ þ PR2 ðtÞN el;DB;R ðR2Þ ; the number of electrons in the four equivalent domains of the nas-
dt
cent single bonds of the products, with equal volumes V SB;P . The
ð46Þ
time evolution of electron transfer from R to P during DBS by tun-
where Nel,DB,R(R1), Nel, DB,R(R2) denote the numbers of electrons in neling – that means four times the absolute value of the negative
the volume V DB;R of the domain of the reactants if the nuclei are yield (52) – is given by the simple cos-type expression, with tunnel-
localized at the configurations R1 or R2 of the reactants, respec- ing period sDBS, cf. Eq. (27). Finally, the flux of electrons out of the
tively. For symmetry reasons, these numbers are the same, i.e., RI four equivalent domains of the double bonds of the reactants, or
between R1 and R2 does not change the numbers of electrons in out of the corresponding domains of the nascent single bonds of
the domains of the double bonds of the reactants. Accordingly, the products, is simply four times the time derivative of the yield
using the unifying notation [39], expression (51), with the same tunneling period sDBS. RI does
Nel;DB;R ¼ Nel;DB;R ðR1Þ ¼ Nel;DB;R ðR2Þ; ð47Þ not affect these overall results for the electron flux during the peri-
cyclic reaction of COT in the tunneling domain. Nevertheless, both
together with Eq. (40), we obtain RI and DBS are important if one monitors the population of a spe-
cific reactant or product, say R1, cf. Eqs. (35)–(38).
d
F el;DB;R ðt; AÞ ¼ Nel;DB;R P R ðtÞ
dt
2.5. Transfer of electrons in pericyclic orbitals, other valence orbitals,
¼ Nel;DB;R ðDEDBS p=hÞ sinð2DEDBS pt=hÞ and core orbitals during the pericyclic rearrangement of COT in the
1 tunneling limit
¼  N el;DB;R ðDEDBS =hÞ sinðDEDBS t=hÞ: ð48Þ
2
Likewise, RI between the products P1 and P2 does not change the The one-electron densities qel,R(r; RR1), qel,R(r; RR2), qel,R(r; RP1),
numbers of electrons in any of the four domains of the carbon–car- qel,R(r; RP2) for the four different configurations R1, R2, P1 and P2
bon single bonds of the nascent products, with volume V SB;P . Hence, of COT are calculated with the MOLPRO program [41]. To obtain
using accurate results, a multi-reference configuration interaction
Z (MRCI) calculation with Davidson correction was performed on
Nel;SB;P ¼ N el;SB;P ðP1Þ ¼ Nel;SB;P ðP2Þ  dV qel;R ðr; RP1 Þ top of a CAS (8, 8) calculation including the electrons of p-charac-
V SB;R ter. A cc-pVTZ basis set was used [42]. The structure obtained after
Z
geometry optimization in D2d-symmetry compares very well with
¼ dV qel;R ðr; RP2 Þ; ð49Þ the experimental data of Ref. [32], with calculated structure param-
V SB;R
eters d(CAC) = 147.8 pm, d(C@C) = 134.0 pm, d(CAH) = 106.9 pm,
together with Eq. (41) yields \(CACAC) = 2.205 rad, \(HAC@C) = 2.058 rad and \(HACAC) =
d 2.018 rad. The corresponding angles between the intersecting
F el;SB;P ðt; AÞ ¼ Nel;SB;P PP ðtÞ boundaries for double and single bonds are \(CAC) = 0.753 and
dt
\(C@C) = 0.818 rad, respectively. The ratio of the volumes are thus
1
¼ Nel;SB;P ðDEDBS =hÞ sinðDEDBS t=hÞ; ð50Þ
2 V SB \ðC  CÞ
¼ ¼ 0:920; ð54Þ
for the contribution of the electronic flux during the pericyclic reac- V DB \ðC ¼ CÞ
tion R ? P, out of any of the four single bond domains of the nascent
products, with volume V ¼ V SB;P . Inserting (48) and (50) into (45) different from the ratio of the (tilted) bond lengths, d(CAC)/
yields the final result, d(C@C) = 1.103.
For further investigation, the densities may be decomposed into
1 three contributions: Electrons occupying ‘‘pericyclic” (peri) orbitals
F el ðt; AÞ  ðN el;SB;P  Nel;DB;R ÞðDEDBS =hÞ sinðDEDBS t=hÞ: ð51Þ
2 which correspond to the active orbitals of the CAS calculation,
The difference Nel,SB,P  Nel,DB,R accounts for the transformation of other valence (oval) orbitals, and core (core) electrons which are
the double bond of R into the single bond of P, during the pericyclic the 1s orbitals of the carbon atoms, for example
reaction. The resulting (negative) yield – that means loss – of the
electrons which leave the domain of the initial double bond is [39] qel;R ðr; RR1 Þ ¼ qel;R;peri ðr; RR1 Þ þ qel;R;oval ðr; RR1 Þ
Z t þ qel;R;core ðr; RR1 Þ: ð55Þ
0
Y el ðt; AÞ ¼ dt F el ðt 0 ; AÞ
0
1 Essentially, the pericyclic orbitals are the ones which correspond to
 ðNel;SB;P  Nel;DB;R Þð1  cosðDEDBS t=hÞÞ: ð52Þ different Lewis structures R and P of COT, cf. Fig. 1. The two contri-
2
butions for pericyclic and other valence electrons add up to the
The factor (1  cos(DEDBSt/⁄)) describes the effects of periodic electron density of the electrons in all the valence orbitals,
coherent tunneling R ? P ? R ? P ? etc., with period sDBS. In par-
ticular, for t = sDBS/2, when all the reactants R (=R1 or R2) have tun- qel;R;val ðr; RR1 Þ ¼ qel;R;peri ðr; RR1 Þ þ qel;R; oval ðr; RR1 Þ: ð56Þ
neled to products P (=P1 or P2) by DBS, the (negative) yield of
electrons which flow out of any of the four equivalent domains is Equivalent expressions apply to qel,R(r; RR2), qel,R(r; RP1) and
equal to the extreme value qel,R(r; RP2). All electron densities were calculated on a grid of
Y el ðsDBS =2; AÞ ¼ Nel;SB;P  Nel;DB;R : ð53Þ 440  440  440 points with grid spacing of 2.6 pm.
The decomposition (55) carries over to corresponding defini-
Eqs. (51)–(53) allow illuminating interpretations. Accordingly, the tions of the numbers of periyclic, other valence, core, or valence
maximum number of electrons which are transferred by tunneling electrons, e.g.
via DBS from R (irrespective of the conformations R1 or R2) to P
(irrespective of the conformations P1 or P2) – that means four times Nel;DB;R;k ¼ Nel;DB;R;k ðR1Þ ¼ Nel;DB;R;k ðR2Þ; ð57Þ
52 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55
for k = peri, oval, core, val cf. Eq. (47); to the resulting fluxes (c.f. Eq.
(51)),
1
F el;k ðt; AÞ  ðNel;SB;P;k  Nel;DB;R;k ÞðDEDBS =hÞ sinðDEDBS t=hÞ;
2
and to the (negative) yields (that means losses) of electrons which
flow out of the domain of the double bonds of the reactants, or out
of the domains of the single bonds of the nascent products, (cf. Eq.
(52)),
1 1
Y el;k ðt; AÞ  ðNel;SB;P;k  Nel;DB;R;k Þð1  cosðDEDBS t=hÞÞ:
2
In particular, it will be interesting to use the results for the extreme
values of the electron yields (c.f. Eq. (53))
Y el;k ðsDBS =2; AÞ  Nel;SB;P;k  Nel;DB;R;k ;
for a quantification of the rules based on curved arrows in the Lewis
structure of the reactant: How many electrons flow out of each of
the four equivalent domains for double bonds of the reactant?
3. Results and discussions
In order to answer the questions which have been raised in Sec-
tion 1 about the electron fluxes during the pericyclic rearrange-
ment of COT in the tunneling limit, we first note that the validity
of the BOA implies that the electronic wavefunction wel(q,Q) of
the non-degenerate electronic ground state, Eq. (1), is real-valued.
As a consequence, the mean value of electronic angular momen-
tum for rotations around the C2 axis is zero. This is in accord exclu-
sively with the pincer-motion-type flux of electrons, which is
illustrated in the middle of the left hand side (lhs) of Fig. 1. In con-
trast, the familiar clockwise or counter-clockwise fluxes of elec-
trons, which are illustrated schematically in the top and bottom
versions of the lhs of Fig. 1, have opposite, non-zero mean values
of angular momenta. Hence, they are ruled out for the pericyclic
rearrangement of COT in the electronic ground state. They remain
options, however, for electron fluxes in excited states, cf. Refs.
[19,43–46].
The representation of the pincer-motion-type flux of electrons
by eight single headed curved arrows in the Lewis structure of
COT (cf. Fig. 1) implies that out of each of the four domains of
the double bonds, part of the pericyclic electrons flow clockwise
through one of the half plane boundaries, while the same amount
of electrons flow counter-clockwise through the opposite half
plane boundary; see the definitions in the beginning of Section 2.4.
Next we address the question of how many electrons actually
flow. For this purpose, we evaluate the electron yields and fluxes,
cf. Eqs. (51)–(53) for all electrons as well as (58)–(60) for the elec-
trons in pericyclic, other valence, all valence and in core orbitals.
According to the derivation of Section 2, the results depend, in part,
on the probabilities PR(t) and PP(t) of observing COT as reactant R
and product P, in the tunneling limit, cf. Eqs. (40), (41), (43)–
(53). These probabilities are illustrated in Fig. 4, together with
the probabilities PR1(t), PR2(t) and PP1(t), PP2(t) of observing COT
as reactants R1, R2, or products P1, P2, if the pericyclic rearrange-
ment starts out from reactants R1. As anticipated, on one hand,
PR(t) and PP(t) display periodic, slow tunneling R ? P ? R ?
P ? etc. with tunneling time sDBS due to DBS, Eq. (27), without
any effect of RI. On the other hand, the individual components
R1, R2 of R and P1, P2 of P show the same overall time evolutions
due to DBS as envelope, but this is modulated by the much faster
tunneling by ring inversions of the reactant (RIR), R1 ? R2 ?
R1 ? R2 ? etc. as well as of the products (RIP) P1 ? P2 ?
P1 ? P2 ? etc., respectively, with tunneling time sRI, Eq. (29).
The ratio of the tunneling times sRI/sDBS can be estimated, in
zero order approximation, by means of the semiclassical theory
1
PR1
ð58Þ 0
1
PR2
0
ð59Þ
P1
P
0
1
ð60Þ
PP2
0
0 0.5 1 1.5
t/τ
DBS
Fig. 4. Probabilities (a) PR1(t), (b) PR2(t), (c) PP1(t), (d) PP2(t) of observing the
reactants R1, R2, or the products P1 or P2, if COT has been prepared initially as R1,
cf. Eqs. (35)–(38), respectively. The envelope of PR1(t) and PR2(t) is the probability
PR(t) of observing the reactants R, Eq. (40). Likewise, the envelope of PP1(t) and PP2(t)
is the probability PP(t) of observing the products P, Eq. (41). The slowly varying PR(t)
and PP(t) indicate coherent tunneling R ? P ? R ? P ? etc. by DBS. The rapid
modulations of PR1(t) and PR2(t), or PP1(t) and PP2(t) indicate much faster coherent
tunneling R1 ? R2 ? R1 ? R2 ? etc. or P1 ? P2 ? P1 ? P2 ? by RIR or RIP of the
reactants and products, respectively. The ratio of the tunneling times sDBS/sRI = 5.3
is adapted from the estimate (61).
of Miller [47], see also Ref. [26]. For this purpose, we design exem-
plary RI and DBS tunneling paths from the potential minimum rep-
resenting R1 via VRI to R2, and from R1 via VDBS to P2, respectively.
The lengths of the two tunneling paths are about equal, i.e., ca. 1.7
a0, cf. Fig. 2. For the barrier heights, we adapt the values VDBS = 55.2
and VRI = 51.9 kJ/mol [32], cf. Eq. (32). For comparison, the present
MRCI calculation yields VDBS = 86.5 kJ/mol and VRI = 55.6 kJ/mol,
respectively. A detailed comparison of the results for various quan-
tum chemical methods will be presented elsewhere. For a simple,
crude estimate, the profiles of the PES along these tunneling paths
are fitted as symmetric polynomials Vtun,RI and Vtun,DBS of fourth or-
der to these parameters. The reduced masses l for motions along
these tunneling paths are the same, l = 2(mC + mH), because
four fragments CH move versus the other four fragments CH during
RI as well as during DBS. The ratio of the tunneling times is then
[47]
sDBS
¼ 5:3: ð61Þ
sRI
This ratio is used in Fig. 4, see the rapid modulations of the proba-
bilities PR1(t) etc. due to RI, compared to the rather slow variation of
the envelope representing PR(t), due to DBS. The subsequent results
will be expressed in terms of sDBS, see Figs. 4, 6, irrespective of the
numerical value of sDBS. For example, sDBS = 1.9  106 s for the sim-
ple model of Ref. [47]. More sophisticated theories of multidimen-
sional tunneling may yield different values, but this is irrelevant
for the subsequent conclusions [48,49].
The results for the electron fluxes and yields also depend on the
difference of the number of electrons in one of the sectors for the
double bonds of the reactants, minus the number of electrons for
the sector of the single bonds of the nascent products, see Eqs.
(51)–(53) for all electrons as well as Eqs. (58)–(60) for the parti-
tioning of the electrons into pericyclic, other valence, and core
electrons, see the derivation in Sections 2.4 and 2.5, respectively.
These numbers are evaluated, in principle, as integrals of the
 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55 53

corresponding one-electron densities in the sectors for double (R)
and single (P) bonds, respectively. The one-electron densities are
illustrated by transparent perspective three-dimensional (3d) equi-
density contour plots of the densities qel,k(r;RR1) and qel,k(r;RR2),
k = peri and val, for the reactants R1 and R2, in the upper and lower
left panels of Fig. 5, respectively. The upper and lower middle
panels of Fig. 5 show corresponding bird’s eye views of the same
one-electron equidensities of R1 and R2, which can tunnel one to
another by RIR. Obviously, these bird’s eye views look the same,
due to the symmetry of R1 and R2. This confirms that the corre-
sponding integrated numbers of electrons in one of the sectors
for double bonds are the same for R1 and R2, Eqs. (47), (57). Like-
wise, Fig. 5 shows two bird’s eye views of the electron densities for
the products P1 and P2, with indications of the corresponding
tunnelings by RIP, and by DBS. Again, they look the same due to
the symmetry of P1 and P2. This confirms that the corresponding
integrated numbers of electrons in the sectors for the nascent sin-
gle bonds are the same for P1 and P2, cf. Eq. (49).
Obviously, the bird’s eye views of P1 and P2 look the same as
those of R1 and R2, except for a rotation by p/4. This shows that
the numbers Nel,SB,P or Nel,SB,P,k of the electrons in the sectors with
single bonds of the nascent products (subscript P) are the same as
the numbers of electrons in the corresponding sectors of single
bonds of the reactant (subscript R),
Nel;SB;R ¼ N el;SB;P ;
Nel;SB;R;k ¼ Nel;SB;P;k for k ¼ peri; oval; val; core:
Eqs. (62), (63) yield simple relations of the numbers of electrons in
sectors for single and double bonds. For example, COT has the total
number of electrons Nel = 56, hence
Nel ¼ 56 ¼ 4ðN el;DB;R þ N el;SB;P Þ;
thus
Nel;DB;R  Nel;SB;P ¼ 2Nel;DB;R  56=4 ¼ 0:47:
Likewise, the numbers of electrons in pericyclic, other valence, all
valence and in core electrons are Nperi = 8, Noval = 32, Nval = 40 and
Ncore = 16. As a consequence,
Nel;DB;R;peri  Nel;SB;P;peri ¼ 2Nel;DB;R;peri  8=4 ¼ þ0:37; ð66Þ
Nel;DB;R;oval  Nel;SB;P;oval ¼ 2Nel;DB;R;oval  32=4 ¼ 0:86; ð67Þ
Nel;DB;R;val  Nel;SB;P;val ¼ 2Nel;DB;R;val  40=4 ¼ 0:49; ð68Þ
Nel;DB;R;core  Nel;SB;P;core ¼ 2Nel;DB;R;core  16=4 ¼ 0:02: ð69Þ
TThe values which are listed in Eqs. (65)–(69) are obtained by cor-
responding integrations of the one electron densities qel,R(r;RR1) or
qel,R,k(r;RR1), k = peri,oval,val,core, in one of the sectors for double
bonds of the reactant R, cf. Fig. 5. In fact, Eqs. (65)–(69) show that
in order to calculate the differences of the numbers of electrons in
the sectors for double bonds of the reactants minus the numbers
of electrons in the sectors for nascent single bonds of the products,
readily for calculations of the electron fluxes and yields, cf. Eqs.
(51)–(53) and (58)–(60), all one needs is the corresponding num-
bers of electrons in the sectors for double bonds, together with
the total number of electrons or the overall number of electrons
in the corresponding set of orbitals. The results (66)–(69) are con-
sistent with (65). The resulting time evolutions of the partial elec-
tron yields Yel,k(t, A) as well as the related fluxes Fel,k(t, A), cf. Eqs.
(58)–(60), are illustrated in Fig. 6, for k = peri, oval and core.
Let us first discuss the results for the electron yields Yel,k(sDBS/
2, A), starting with the electrons in pericyclic orbitals (k = peri),
Yel,peri(s DBS/2, A)  0.37. Apparently, the absolute value of
Yel,peri(sDBS/2, A) is much smaller than the number 2 which one
may assign to the curved arrows in the Lewis structure, for refer-
ð62Þ ence, see Fig. 1. The reason for this significant reduction from 2
ð63Þ to only j  0.37j is that the Lewis structure symbolizes, for simplic-
ity and for reference, the case when the electrons undergoing DBS
are localized initially exclusively in the double bonds. In contrast,
the present quantum simulations show that the electrons are delo-
calized not only in the domains of double bonds, but also in single
bonds, see Fig. 5. Considering the four double bonds of the reactant,
ð64Þ it suffices, therefore, that just 4  0.37 = 1.48, not 4  2 = 8 pericy-
clic electrons participate in double bond shifting. Another idea is to
compare the value 1.48 with the number of electrons in the highest
occupied molecular orbital (HOMO) which is related to DBS. How-
ð65Þ ever, on one hand in post Hartree–Fock methods the concept of the
HOMO is not applicable, and on the other hand on Hartree–Fock le-
vel this would still be an overestimation.
The simple model of curved arrows in Lewis structures does not
consider any electrons in other valence (k = oval) orbitals. In

Fig. 5. Equidensity contours for electrons in pericyclic orbitals (orange/ red, qel,R,peri = 0.04 and 0.4 a3 3
0 ), in all valence orbitals (blue/ green, qel,R,val = 0.27 and 0.53 a0 ) and for
all electrons (grey, qel,R = 0.05 a3
0 ), together with stick-and-ball plots of COT in the configurations of the reactants R1 and R2 (left and middle panels) and products P1 and P2
(right panels). The left panels show three-dimensional perspective views, whereas the middle and right panels show birds’ eye views. Also indicated are the two ring
inversions RIR and RIP of the reactants R and products P, as well as the double bond shifting DBS between R and P. The grey-shaded sectors correspond to one of the four
equivalent domains of double bonds (for R1) and single bonds (for P1), respectively (compare Fig. 1). The graphical representations have been generated using the AMIRA
package [50].
54 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55
Y flux of electrons goes from the domains of single bonds to double
0.6 el,core
Y
yield
el,oval
Yel,peri
−0.6
Fel,core
0.3
F bonds. The second contribution is due to electrons in pericyclic
el,oval
flux
F
el,peri
−0.3
0 0.5 1 1.5
t/τ
DBS
Fig. 6. (a) Partial yields Yel,k(t, A) of electrons in pericyclic (k = peri), other valence
(k = oval) and core electrons (k = core), which leave one of the sectors for a double
bond of COT through its boundary (A), cf. Eq. (59). (b) The corresponding partial
electron fluxes Fel,k(t, A), cf. Eq. (58).
contrast, quantum chemistry yields the result Yel,oval (sDBS/2, A) 
+0.86. Surprisingly, this contribution to the overall yield Yel(sDBS/
2, A) is positive, i.e., the pericyclic electrons flow in the direction
opposite to the electrons in other valence orbitals. These trends
can be rationalized as follows. The electrons in the complementary
valence electrons are dominated by the electrons occupying the
CH-r-bonds. Essentially, these travel from the domain of the single
bonds of the reactants to the single bonds of the nascent products,
cf. Figs. 1 and 4.
As expected, the flux due to the electrons in the 1s electrons of
the carbon nuclei (k = core) is negligible, Yel, core(sDBS/2,A)  0.02.
Summing up, the electron yield of all valence electrons is
Y el;val ðsDBS =2; AÞ ¼ Y el;peri ðsDBS =2; AÞ þ Y el;oval ðsDBS =2; AÞ
¼ 0:37 þ 0:86 ¼ 0:49; ð70Þ
i.e., the flux of pericyclic electrons is compensated by the antagonis-
tic flux of all other valence electrons, mainly by the electrons occu-
pying the 1s orbitals of the hydrogen atoms. Finally, the total
electron yield is
Y el ðsDBS =2; AÞ ¼ Y el;val ðsDBS =2; AÞ þ Y el;core ðsDBS =2; AÞ
¼ 0:49  0:02 ¼ þ0:47: ð71Þ
Accordingly, the total number (= 0.47) of electrons which are trans-
ferred during the pericyclic rearrangement of COT in the domain of
coherent tunneling is about equal to the absolute value of the peri-
cyclic electrons (= j0.37j), but with opposite sign, i.e., the net flux
of electrons during DBS by tunneling is not out of, but into the do-
mains of double bonds of the reactant.
Fig. 6 shows the corresponding time evolutions of the electron
yields and fluxes during pericyclic rearrangement of COT in the tun-
neling limit. As anticipated in Section 2.5, Eqs. (58) and (59), all the
individual Yel,k(t, A) and Fel, k(t, A) have the same time evolutions
(1  cos(t/sDBS) and sin(t/sDBS) depending on the tunneling time
by DBS, without any influence of RIR or RIP. The opposite directions
of the fluxes of the electrons in pericyclic orbitals compared to other
valence and core orbitals, as well as the quantitative dominance of
the flux in other valence orbitals, are obvious from Fig. 6b.
4. Conclusions
The present results for electron fluxes during pericyclic rear-
rangement of COT have been derived for the ideal situation of
coherent tunneling. The results are surprising, that means the net
bonds of the reactants, or to the nascent single bonds of the prod-
ucts, not vice versa, as implied by the traditional arrows in Lewis
structures. The apparent paradox has been analyzed by decompo-
sition of the net flux into three components. It turns out that a
dominant contribution stems from the r-bonds of the CH groups
which travel with the protons of the hydrogen atoms, or in general
it stems from other valence electrons which are not directly in-
volved in double bond shifting of COT: all these components of
the net electron flux flow from the domains of single to double
orbitals, that means those orbitals which are involved in the
changes of the Lewis structures from reactants to products: These
pericyclic components do indeed flow from the domains of double
to single bonds of the reactants, as symbolized by the arrows in Le-
wis structures. Quantitatively, the flux of pericyclic electrons out of
the four equivalent domains of double bonds is about as large – or
should one better say ‘‘as small” (=0.37  4 = 1.48) as the net
flux of electrons into these domains (=+0.47  4 = +1.88), but with
opposite signs,  and +, respectively. The analogous effect, that
means opposite fluxes of electrons in orbitals with p-character
compared to orbitals with r-character during pericyclic proton
transfer in formamide, at energies well above the tunneling do-
main, has been discovered first by Nagashima and Takatsuka [19].
The quantitative results depend on the definition of the domain
boundaries. The sensitivity with respect to variation of the bound-
aries will be discussed elsewhere. We anticipate that the results
will be robust for electrons in delocalized pericyclic and other
valence orbitals. In contrast, shifts of the boundaries away from
the carbon nuclei may affect the results for electrons in core
orbitals, which are localized close to the nuclei.
It is a challenge to extend the present investigations to pericy-
clic rearrangements of COT at finite temperatures, comparable to
the experimental situations of Refs. [14,22–25,27,28,32]. As a
working hypothesis, the overall findings, which have been summa-
rized in the first paragraph of this conclusions section, will be ro-
bust, because they may be derived from exclusive quantum
chemical evaluations of the one electron densities of the reactants
and products, irrespective of the quantum dynamical details. That
means, for example, that we expect the same overall trends of
antagonistic fluxes of electrons in pericyclic versus all other orbi-
tals, if the pericyclic rearrangement of COT proceeds at finite e.g.
room temperature.
It will also be a challenge to extend the present investigations to
pericyclic reactions of other systems. Will the trend of opposite
directions of the fluxes of electrons in pericyclic versus all other
orbitals be confirmed, again from the tunneling limit to reactions
say at room temperature? If so, a very important goal will be to
gain a deeper understanding of the undoubted success of the rules
of arrows in Lewis structures for predicting the course of pericyclic
reactivity [1–11]. The present results already suggest a working
hypothesis, i.e., pericyclic reactivity is governed by electrons in
pericyclic orbitals, irrespective of the even larger opposite fluxes
of electrons in other valence orbitals. The deeper understanding
may well reveal a late triumph of the ingenious power of the sym-
bolic arrows in Lewis structures, i.e., they focus on the essentials, at
least qualitatively. Work along these lines is in progress.
Acknowledgements
We are very grateful to Professor H. Kono and Dr. K. Hoki
(Tohoku University Sendai), Professor K. Takatsuka (Tokyo Univer-
sity) as well as Dr. R. Flesch (Freie Universität Berlin) for helpful
discussions. We would also like to thank our colleagues from Or-
ganic Chemistry, Professors H. Ikeda (Osaka Prefecture University),
 H.-C. Hege et al. / Chemical Physics 376 (2010) 46–55 55

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