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J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct
Department of Chemistry, and Mathematical Modeling and Computational Science Center (LMCC), Katholieke Universiteit Leuven, B-3001Leuven, Belgium
Institute of Chemistry, Vietnam Academy of Science and Technology, Hanoi, Viet Nam
a r t i c l e
i n f o
Article history:
Received 9 July 2009
Received in revised form 15 October 2009
Accepted 23 October 2009
Available online 29 October 2009
Keywords:
Caffeine
Theophylline
Xanthine
Uracils
Imidazoles
Heats of formation
Ionization energies
Quantum chemical calculations
a b s t r a c t
Thermochemical parameters of caffeine 1, theophylline 2, xanthine 3, uracil, and imidazole derivatives
are determined by quantum chemical calculations. Using the composite G3B3 method, the standard heat
1
of formation of caffeine in the gaseous phase amounts to Df Hg 1 243 8 kJ mol , which lends a
1
support for the recent experimental value of 237.0 2.5 kcal mol . We also obtain Df Hg 2
1
1
232 8 kJ mol and Df Hg 3 209 8 kJ mol . The adiabatic ionization energies are IEa(1) =
7.9 eV, IEa(2) = 8.1 eV, and IEa(3) = 8.5 eV using B3LYP calculations. The enhanced ability of caffeine to
eject electron, as compared to the parent compounds and cyclic components, is of interest with regard
to its potential use as a corrosion inhibitor.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Caffeine 1 (scheme 1) is a biologically active substance and exerts many pharmacological effects on the human body. It is rmly
established in the popular culture as a stimulant for the central
nervous system, and therefore it is omnipresent and consumed
every day by billions of people from a variety of foods and drinks.
In low concentrations, caffeine inhibits the adenosine moiety of the
cyclic adenosine monophosphate (c-AMP) to bind to its receptor,
but at high concentrations, it becomes an inhibitor of phosphodiesterase [1,2].
Caffeine can play the role of an effective antioxidant, in particular in the scavenging of the hydroxyl radical [3,4]. 1 was proved to
be a good indicator in analytical methods to detect microbes in
surface waters [5], or potentially useful starting reagent in the synthesis of N-heterocyclic carbenes [6]. More interestingly, 1 has
been proved to be a promising inhibitor against the corrosion process of many metal and alloys [79]. The use of natural organic
compounds such as caffeine and green tea to protect metals from
corrosion is particularly attractive, because they are both economic
and environment-friendly. The effect likely arises from their ability
to induce strong adsorption onto the metal surface, which prevents
the latter from undergoing oxidation reactions.
Caffeine can be extracted not only from coffee and cocoa beans,
but also from green tea leaves, etc. In view of its popularity,
chemical properties and reactions of caffeine have much been
investigated during the last two centuries. Its structural and spectroscopic parameters were well determined. Its molecular geometry was determined by crystal structure analysis [10,11] and its
various spectra in different forms well recorded and assigned
(infrared: [12,13], UVvisible: [1416], He I photoelectron: [17],
and photoionization: [18]).
Although the thermochemical parameters of caffeine have been
the subject of a number of studies [1932], some fundamental values remain the subject of recent debate. The experimental values
previously determined for the sublimation enthalpy of 1 in the
crystal phases vary from (104 to 117) kJ mol1. For the standard
enthalpy of formation of caffeine in the crystal phase, Pinto and
Diogo [30] derived from combustion experiments the values of
(345.1 2.3 and 340.6 2.3) kJ mol1, the both a and b phases,
respectively. Subsequently, Dong et al. [31] obtained by using
bomb combustion calorimetry in oxygen, a value of 322.2
4.8 kJ mol1 for this quantity in the a-phase, which thus differs
signicantly from the earlier results [30]. More recently,
Emelyamenko and Verevkin [32] redetermined the heat of sublimation of 1 using the transpiration method, and their results were
more consistent with those of Pinto and Diogo [30].
Using the set of enthalpies of formation and sublimation in the
crystal phase reported in references [30,32], the standard enthalpy
of formation in the gaseous phase Df Hg 1 can be evaluated to be
438
SCHEME 1.
439
TABLE 1
Total atomization energy (RD0), heats of formation (DfHg at 0 K and 298 K), vertical (VIE), and adiabatic (AIE) ionization energies of caffeine, theophylline, and xanthine and
derivatives.
Species
Caffeine 1
Caffeine cation 1+
Theophylline 2
Theophylline cation 2+
Xanthine 3
Xanthine cation 3+
Uracil 4
+
Uracil cation 4
Methyluracil 5
Methyluracil cation 5+
Imidazole 6
Imidazole cation 6+
N-methylmidazole 7
N-methylmidazole
Cation 7+
a
b
c
d
e
f
g
Electronic
state
RD0/
DfHg 0 K,
G3B3/(kJ mol1)
DfHg 298 K
G3B3/(kJ mol1)
DfHg exptl
298 K/(kJ mol1)
VIEcalc
B3LYP/eV
AIEcalc
G3B3/eV
AIEcalc
B3LYP/eV
VIEexptl/eV
(kJ mol1)
10437.8
9666.0
9289.2
8498.4
6989.9
6154.7
5427.2
202.8
568.9
197.5
593.3
184.6
650.6
274.8
243.4
526.2
231.7
559.2
208.8
626.3
294.0
237.0 2.5
8.06
8.00
7.87
8.25a
8.27
8.20
8.07
8.74
8.66
8.51
8.84a
303.1 2.3b,c
9.52
9.35
9.21
4524.7
7723.7
6876.1
3789.3
2936.8
4935.3
4110.2
627.7
284.8
562.8
150.1
1002.5
147.2
972.4
608.8
314.2
533.7
134.0
986.6
126.0
949.5
313.6 1.5c,d
8.84
8.79
8.62
132.9e 133.0
993.8f
137.8 4g
8.99
8.84
8.71
8.96c
8.78
8.55
8.43
8.66c
A0
A00
1 0
A
2 00
A
1 0
A
2 00
A
1 0
A
2
00
A
A0
2 00
A
1 0
A
2 0
A
1 0
A
2 00
A
1
Reference [18].
Reference [42].
Reference [41].
Reference [45].
Reference [35,36].
Reference [38].
Reference [42].
formation at 0 K. Table 1 also includes the available experimental values for comparison.
For imidazole 6, the simplest species considered, the G3B3 value of 134.0 kJ mol1 for its heat of formation at 298 K compares
indeed quite well with the experimental results of 132.9
0.6 kJ mol1 [35] and 133.0 1.7 kJ mol1 [36]. A recent study
using coupled-cluster CCSD(T) theory with extrapolated complete
basis set (CBS) obtained a value of 132.2 kJ mol1 [37]. On the
contrary, the G3B3 value for the radical cation 6+ deviates by
6 kJ mol1 with respect to the experimental results [38]. This is
however in line with the performance of various theoretical methods for both VIE and AIE of imidazole [39]. In this case, the B3LYP
value of 8.71 eV for AIE(6) is closer to the photoelectron result of
8.67 eV [39,40] than the G3B3 value of 8.84 eV. The B3LYP value
for VIE(6) compares also quite good with experiment [41]. It appears that the IEs determined from B3LYP calculations are systematically smaller by 0.15 eV than those from G3B3 heats of
formation. This suggests that the heats for formation of the radical
cations are underestimated by a similar amount. This is likely due
to the spin contamination in the UHF wavefunctions that slows
down the convergence of the MPn and QCISD expansions in the
G3 approach.
For N-methylimidazole 7, the G3B3 heat of formation is
126.0 kJ mol1 at 298 K, ca. 12 kJ mol1 less endothermic than
the experimental value of 137.8 4 kJ mol1 determined by Mo
and co-workers [42]. This value is closer to the values obtained
by using the total atomization energies of (128.5 and 125.1) kJ
mol1 at the G2(MP2) and B3LYP/6-311+G(3df,2p)//B3LYP/631G(d) levels, respectively, than those obtained using quasiisodesmic reactions, namely 132.6 (G2MP2) and 138.5 kJ mol1,
B3LYP/6-311+G(3df,2p) [42]. The agreement of the calculated VIE
is also in the order of 0.1 eV. It appears that an N-methylation
of the ve-membered ring reduces its ionization energy by
0.2 eV.
The G3B3 value of 294.0 kJ mol1 for DfH (298 K) of uracil 4 is
underestimated by 9 kJ mol1 with respect to the NIST value
[41,43] (table 1) but closer to an earlier theoretical estimate of
295.4 kJ mol1 [44]. On the contrary, the values for AIE(4) of
(9.2 to 9.3) eV compare well with the experimental result of
440
[11]
[12]
[13]
[14]
[15]
JCT 09-243