Presence and absence of excited state intramolecular charge transfer with the six isomers of dicyano-N,N-dimethylaniline and dicyano-(N-methyl-N-isopropyl)aniline

The excited state behavior of the six m,n-dicyano-N,N-dimethylanilines (mnDCDMA) and m,n-dicyano-(N-methyl-N-isopropyl)anilines (mnDCMIA) is discussed as a function of solvent polarity and temperature. The dicyano moiety in these electron donor (D)/acceptor (A) molecules has a considerably larger electron affinity than the benzonitrile subgroup in 4-(dimethylamino)benzonitrile (DMABN). Nevertheless, the fluorescence spectra of the mnDCDMAs and mnDCMIAs in n-hexane all consist of a single emission originating from the locally excited (LE) state, indicating that a reaction from LE to an intramolecular charge transfer (ICT) state does not take place. The calculated energies E(ICT), obtained by employing the reduction potential of the dicyanobenzene subgroups and the oxidation potential of the amino substituents trimethylamine (N(Me)(3)) and isopropyldimethylamine (iPrNMe(2)), are lower than E(LE). The absence of an LE → ICT reaction therefore makes clear that the D and A units in the dicyanoanilines are not electronically decoupled. In the polar solvent acetonitrile (MeCN), dual (LE + ICT) fluorescence is found with 24DCDMA and 34DCDMA, as well as with 24DCMIA, 25DCMIA, and 34DCMIA. For all other mnDCDMAs and mnDCMIAs, only LE emission is observed in MeCN. The ICT/LE fluorescence quantum yield ratio Φ'(ICT)/Φ(LE) in MeCN at 25 °C is larger for 24DCDMA (1.2) than for 34DCDMA (0.35). The replacement of methyl by isopropyl in the amino substituent leads to a considerable increase of Φ'(ICT)/Φ(LE), 8.8 for 24DCMIA and 1.4 for 34DCMIA, showing that the LE ? ICT equilibrium has shifted further toward ICT. The appearance of an ICT reaction with the 2,4- and 3,4-dicyanoanilines is caused by a relatively small energy gap ΔE(S(1),S(2)) between the two lowest excited singlet states as compared with the other m,n-dicyanoanilines, in accordance with the PICT model. The observation that the ICT reaction is more efficient for 24DCMIA and 34DCMIA than for their mnDCDMA counterparts is mainly caused by the fact that iPrNMe(2) is a better electron donor than N(Me)(3): E(D/D(+)) = 0.84 against 1.05 V vs SCE. That ICT also occurs with 25DCMIA, notwithstanding its large ΔE(S(1),S(2)), is due to the substantial amino twist angle θ = 42.6°, which leads to partial electronic decoupling of the D and A subgroups. The dipole moments μ(e)(ICT) range between 18 D for 34DCMIA and 12 D for 25DCMIA, larger than the corresponding μ(e)(LE) of 16 and 11 D. The difference between μ(e)(ICT) and μ(e)(LE) is smaller than with DMABN (17 and 10 D) because of the noncollinear arrangement of the amino and cyano substituents (different dipole moment directions). The dicyanoanilines that do not undergo ICT, have LE dipole moments between 9 and 16 D. From plots of ln(Φ'(ICT)/Φ(LE)) vs 1000/T, the (rather small) ICT reaction enthalpies ΔH could be measured in MeCN: 5.4 kJ/mol (24DCDMA), 4.7 kJ/mol (24DCMIA), and 3.9 kJ/mol (34DCMIA). With the mnDCDMAs and mnDCMIAs only showing LE emission, the fluorescence decays are single exponential, whereas for those undergoing an LE → ICT reaction the LE and ICT picosecond fluorescence decays are double exponential. In MeCN at 25 °C, the decay times τ(2) have values between 1.8 ps for 24DCMIA and 4.6 ps for 34DCMIA at 25 °C. Longer times are observed at lower temperatures. Arrhenius plots of the forward and backward ICT rate constants k(a) and k(d) of 25DCMIA in tetrahydrofuran, obtained from the LE and ICT fluorescence decays, give the activation energies E(a) = 4.5 kJ/mol and E(d) = 11.9 kJ/mol, i.e., ΔH = -7.4 kJ/mol. From femtosecond transient absorption spectra of 24DCDMA and 34DCDMA at 22 °C, ICT reaction times τ(2) = 1/(k(a) + k(d)) of 1.8 and 3.1 ps are determined. By combining these results with the data for the fluorescence decays and Φ'(ICT)/Φ(LE), the values k(a) = 49 × 10(10) s(-1) (24DCDMA) and k(a) = 23 × 10(10) s(-1) (34DCDMA) are calculated. An LE and ICT excited state absorption is present even at a pump/probe delay time of 100 ps, showing that an LE ? ICT equilibrium is established.     

The impact of integrated STEM professional development on teacher quality

This study of a state‐funded, 3‐year implementation of an integrated STEM professional development (PD) program for teachers from two middle schools in the midwestern U.S. examined if participants in the PD were enabled to transform their practice and perceptions of STEM. An integrated STEM approach includes a focus on the STEM disciplines, along with leveraging social studies/history and English/language arts as important context and tools for solving society’s biggest challenges. Findings in this study indicated that teachers implemented more effective STEM teaching strategies and had more positive perceptions regarding STEM overall. Further, participants became more aware of their personal needs for resources and support to teach through integrated STEM. Implications for research and practice are discussed.     

Field-asymmetric transverse magnetoresistance in a nonmagnetic quantum-size structure

A new phenomenon is observed experimentally in a heavily doped asymmetric quantum-size structure in a magnetic field parallel to the quantum-well layers — a transverse magnetoresistance which is asymmetric in the field (there can even be a channge in sign) and is observed in the case that the structure has a built-in lateral electric field. A model of the effect is proposed. The observed asymmetry of the magnetoresistance is attributed to an additional current contribution that arises under nonequilibrium conditions and that is linear in the gradient of the electrochemical potential and proportional to the parameter characterizing the asymmetry of the spectrum with respect to the quasimomentum. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 5, 380–385 (10 September 1998)     

A new three-component one pot reaction of trinitromethane, epoxides and alkenes via dinitronitronates: synthesis of highly functionalized 3,3-dinitroisoxazolidines

A novel approach to acyclic alkyldinitronitronates using nucleophilic opening of epoxides with the trinitromethyl anion is presented. The scope and limitations of this synthetic procedure are presented. A series of highly functionalized 3,3-dinitroisoxazolidines were synthesized as mixtures of diastereomers.     

Investigation of valence band structures in Cu-Pd alloys

With the use of a HP 5950 A spectrometer X-ray photoelectron spectra (XPS) of valence band were obtained for Cu-Pd alloys and the density of electron states was calculated by the coherent potential method. It is found that d-resonance states of Pd are present in the alloys containing a high percentage of copper but there are no apparant d-resonance states of Cu in the alloys containing a high percentage of palladium.     

Unsteady mass and energy transfer in binary gas mixtures

Thermodynamic analysis and a theory of unsteady-state process of thermal diffusion and diffusional thermal effect in gas mixtures are presented. A mathematical model for unsteady mass transfer process in gas mixtures is developed.     

Normal forms of quadratic bose operators

We construct a proper canonical transformation that reduces the quadratic Bose operator to a direct sum of finite-dimensional quadratic operators each of which can be reduced by a finite-dimensional canonical transformation to one of the standard forms corresponding to the standard forms of real quadratic Hamiltonians. Translated fromMatematicheskie Zametki, Vol. 61, No. 1, pp. 69–90, January, 1997.     

Necessary conditions for the stability of difference schemes

For difference equations of the form uⁿ⁺=Auⁿ+f ⁿh, n ≤ T/h the necessary condition for stability due to von Neumann is well known; this condition is expressed in terms of the spectrum of the operator A: r(A)≤1+ch. In this note, for a certain class of difference equations, we express this condition in terms of the spectral radius of the symbol of the operator A.