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• 1. [Article] Structure, Dynamics, and Phase Transitions in the Fullerene Derivatives C_{60}O and C_{61}H_{2}

  The effect of perturbing the icosohedral symmetry of C60 by the addition of the side groups -O and -CH2 upon orientational order-disorder and glass transitions in solid C60 has been studied by a combination ...

  Citation × Citation Citation Abstract Copy Title: Structure, Dynamics, and Phase Transitions in the Fullerene Derivatives C_{60}O and C_{61}H_{2} Author: Meingast, C., Roth, G., Pintschovius, L., Michel, R. H., Stoermer, C., Kappes, M. M., Heiney, Paul A., Brard, Laurent, Strongin, Robert M., Smith, Amos B., III Year: 1996 The effect of perturbing the icosohedral symmetry of C60 by the addition of the side groups -O and -CH2 upon orientational order-disorder and glass transitions in solid C60 has been studied by a combination of high-resolution capacitance dilatometry and single-crystal x-ray and powder inelastic neutron scattering. Both fullerene derivatives C60O (epoxide) and C61H2 (6,5-annulene) are shown to undergo a sequence of transitions similar to that found in pure C60, i.e., a first-order orientational ordering transition just below room temperature followed by an orientational glass transition at lower temperatures. Although the exact origin of the glass transition in C61H2 is unclear, the glass transition in C60O has the same origin as that in C60, with a significantly higher degree of order due to a larger energy difference between pentagon and hexagon orientations. The dilatometric data at the glass transition indicate that, in contrast to C60, the ground-state orientation of both C60O and C61H2 molecules is that with the smallest volume, also demonstrating a significant influence of the side groups upon the details of the structure. A possible explanation of these differences in terms of steric effects is proposed. Title: Structure, Dynamics, and Phase Transitions in the Fullerene Derivatives C_{60}O and C_{61}H_{2} Author: Meingast, C., Roth, G., Pintschovius, L., Michel, R. H., Stoermer, C., Kappes, M. M., Heiney, Paul A., Brard, Laurent, Strongin, Robert M., Smith, Amos B., III Year: 1996 The effect of perturbing the icosohedral symmetry of C60 by the addition of the side groups -O and -CH2 upon orientational order-disorder and glass transitions in solid C60 has been studied by a combination of high-resolution capacitance dilatometry and single-crystal x-ray and powder inelastic neutron scattering. Both fullerene derivatives C60O (epoxide) and C61H2 (6,5-annulene) are shown to undergo a sequence of transitions similar to that found in pure C60, i.e., a first-order orientational ordering transition just below room temperature followed by an orientational glass transition at lower temperatures. Although the exact origin of the glass transition in C61H2 is unclear, the glass transition in C60O has the same origin as that in C60, with a significantly higher degree of order due to a larger energy difference between pentagon and hexagon orientations. The dilatometric data at the glass transition indicate that, in contrast to C60, the ground-state orientation of both C60O and C61H2 molecules is that with the smallest volume, also demonstrating a significant influence of the side groups upon the details of the structure. A possible explanation of these differences in terms of steric effects is proposed. Close

• 2. [Article] Existence of High-Order Superlattices in Orientationally Ordered C_{60}

  We correlate the presence or absence of high-order modulated structures in solid C60 with the differential scanning calorimetry signature of the orientational ordering transition and other diagnostic data. ...

  Citation × Citation Citation Abstract Copy Title: Existence of High-Order Superlattices in Orientationally Ordered C_{60} Author: Fischer, J. E., Luzzi, D. E., Kniaź, K., McGhie, A. R., Ricketts-Foot, D. A., Romanow, W. R., Vaughan, Gavin B. M., Li, Dayin, Smith, Allan L., Strongin, Robert M., Cichy, M. A., Bard, Laurent, Smith, Amos B., III Year: 1993 We correlate the presence or absence of high-order modulated structures in solid C60 with the differential scanning calorimetry signature of the orientational ordering transition and other diagnostic data. We have searched for, but not observed, the 2a face-centered cubic structure recently observed in low-temperature electron and single-crystal x-ray diffraction. We conclude that the intrinsic ground state is the previously reported simple cubic structure [space groupPa3¯, a(14 K)=14.06 Å], and that other structures may be stabilized by defects or impurities. Title: Existence of High-Order Superlattices in Orientationally Ordered C_{60} Author: Fischer, J. E., Luzzi, D. E., Kniaź, K., McGhie, A. R., Ricketts-Foot, D. A., Romanow, W. R., Vaughan, Gavin B. M., Li, Dayin, Smith, Allan L., Strongin, Robert M., Cichy, M. A., Bard, Laurent, Smith, Amos B., III Year: 1993 We correlate the presence or absence of high-order modulated structures in solid C60 with the differential scanning calorimetry signature of the orientational ordering transition and other diagnostic data. We have searched for, but not observed, the 2a face-centered cubic structure recently observed in low-temperature electron and single-crystal x-ray diffraction. We conclude that the intrinsic ground state is the previously reported simple cubic structure [space groupPa3¯, a(14 K)=14.06 Å], and that other structures may be stabilized by defects or impurities. Close

• 3. [Article] Unusual Thermal Stability of a Site-Ordered MC60 Rocksalt Structure (M=K, Rb, or Cs).

  X-ray diffraction and differential scanning calorimetry of MxC60, with x∼1 and M=K, Rb, or Cs, reveal an unusual T-dependent phase sequence. A low-symmetry ground state is found, while the high-T limit ...

  Citation × Citation Citation Abstract Copy Title: Unusual Thermal Stability of a Site-Ordered MC60 Rocksalt Structure (M=K, Rb, or Cs). Author: Zhu, Q., Zhou, O., Fischer, J. E., McGhie, Andrew R., Romanow, W. R., Strongin, Robert M., Cichy, M. A., Smith, Amos B., III Year: 1993 X-ray diffraction and differential scanning calorimetry of MxC60, with x∼1 and M=K, Rb, or Cs, reveal an unusual T-dependent phase sequence. A low-symmetry ground state is found, while the high-T limit is an ordered rocksalt structure in which only the octahedral sites are occupied. The unusual high-T stability of this ordered phase is attributed to the entropy of molecular orientational disorder and/or thermal disorder of the alkali-metal ions within the octahedral sites. Unique to KxC60 with x≥1.4, we find at intermediate temperatures an fcc site-disordered lattice gas phase with random occupancy of tetrahedral and octahedral sites, which is thus isostructural with superconducting K3C60. Title: Unusual Thermal Stability of a Site-Ordered MC60 Rocksalt Structure (M=K, Rb, or Cs). Author: Zhu, Q., Zhou, O., Fischer, J. E., McGhie, Andrew R., Romanow, W. R., Strongin, Robert M., Cichy, M. A., Smith, Amos B., III Year: 1993 X-ray diffraction and differential scanning calorimetry of MxC60, with x∼1 and M=K, Rb, or Cs, reveal an unusual T-dependent phase sequence. A low-symmetry ground state is found, while the high-T limit is an ordered rocksalt structure in which only the octahedral sites are occupied. The unusual high-T stability of this ordered phase is attributed to the entropy of molecular orientational disorder and/or thermal disorder of the alkali-metal ions within the octahedral sites. Unique to KxC60 with x≥1.4, we find at intermediate temperatures an fcc site-disordered lattice gas phase with random occupancy of tetrahedral and octahedral sites, which is thus isostructural with superconducting K3C60. Close

• 4. [Article] Structure and Phase Transition of the 6,5-Annulene Isomer of C_{61}H_{2}

  We have used differential scanning calorimetry and x-ray diffraction to study the crystalline phases of the 6,5-annulene isomer of C61H2. At 308 K the methylenated fullerenes are orientationally disordered ...

  Citation × Citation Citation Abstract Copy Title: Structure and Phase Transition of the 6,5-Annulene Isomer of C_{61}H_{2} Author: Lommen, Andrea N., Heiney, Paul A., Vaughan, Gavin B. M., Stephens, Peter W., Liu, Dengfa, Li, Dayin, Smith, Allan L., McGhie, Andrew R., Strongin, Robert M., Brard, Laurent, Smith, Amos B., III Year: 1994 We have used differential scanning calorimetry and x-ray diffraction to study the crystalline phases of the 6,5-annulene isomer of C61H2. At 308 K the methylenated fullerenes are orientationally disordered in a face-centered cubic lattice with lattice parameter 14.19±0.02 Å. Below Tc=290 K the symmetry is lowered to Pa3¯, a simple-cubic structure. At 20 K the lattice parameter is 14.06±0.02 Å, with substantial statistical disorder remaining. The transition temperature in C61H2 is slightly higher than in C60O and higher still than in C60, but the three compounds exhibit orientationally ordering transitions between qualitatively similar phases. Title: Structure and Phase Transition of the 6,5-Annulene Isomer of C_{61}H_{2} Author: Lommen, Andrea N., Heiney, Paul A., Vaughan, Gavin B. M., Stephens, Peter W., Liu, Dengfa, Li, Dayin, Smith, Allan L., McGhie, Andrew R., Strongin, Robert M., Brard, Laurent, Smith, Amos B., III Year: 1994 We have used differential scanning calorimetry and x-ray diffraction to study the crystalline phases of the 6,5-annulene isomer of C61H2. At 308 K the methylenated fullerenes are orientationally disordered in a face-centered cubic lattice with lattice parameter 14.19±0.02 Å. Below Tc=290 K the symmetry is lowered to Pa3¯, a simple-cubic structure. At 20 K the lattice parameter is 14.06±0.02 Å, with substantial statistical disorder remaining. The transition temperature in C61H2 is slightly higher than in C60O and higher still than in C60, but the three compounds exhibit orientationally ordering transitions between qualitatively similar phases. Close

• 5. [Article] Coherence Peak and Superconducting Energy Gap in Rb_{3}C_{60} Observed by Muon Spin Relaxation

  Muon spin relaxation resulting from spin exchange scattering of endohedral muonium (μ+e-) with thermal electronic excitations has been observed in the fullerene superconductor Rb3C60. The temperature dependence ...

  Citation × Citation Citation Abstract Copy Title: Coherence Peak and Superconducting Energy Gap in Rb_{3}C_{60} Observed by Muon Spin Relaxation Author: Kiefl, R. F., MacFarlane, W. A., Chow, K. H., Dunsiger, S., Duty, T. L., Johnston, T. M. S., Schneider, J. W., Sonier, J., Brard, Laurent, Strongin, Robert M., Fischer, J. E., Smith, Amos B., III Year: 1993 Muon spin relaxation resulting from spin exchange scattering of endohedral muonium (μ+e-) with thermal electronic excitations has been observed in the fullerene superconductor Rb3C60. The temperature dependence of T1-1 shows a coherence peak just below Tc and can be fit to the conventional Hebel-Slichter theory for spin relaxation in a superconductor with a broadened BCS density of states. The average energy gap for electronic excitations, Δ/kB=53(4) K or 2Δ/ kBTc=3.6(3), is consistent with the BCS weak coupling limit. Title: Coherence Peak and Superconducting Energy Gap in Rb_{3}C_{60} Observed by Muon Spin Relaxation Author: Kiefl, R. F., MacFarlane, W. A., Chow, K. H., Dunsiger, S., Duty, T. L., Johnston, T. M. S., Schneider, J. W., Sonier, J., Brard, Laurent, Strongin, Robert M., Fischer, J. E., Smith, Amos B., III Year: 1993 Muon spin relaxation resulting from spin exchange scattering of endohedral muonium (μ+e-) with thermal electronic excitations has been observed in the fullerene superconductor Rb3C60. The temperature dependence of T1-1 shows a coherence peak just below Tc and can be fit to the conventional Hebel-Slichter theory for spin relaxation in a superconductor with a broadened BCS density of states. The average energy gap for electronic excitations, Δ/kB=53(4) K or 2Δ/ kBTc=3.6(3), is consistent with the BCS weak coupling limit. Close

• 6. [Article] Pressure-induced insulating state in an organic superconductor

  The electronic-transport properties of the quasi-two-dimensional organic superconductor β″–(BEDT-TTF)₂SF₅CH₂CF₂SO₃, where BEDT-TTF stands for bisethylenedithio-tetrathiafulvalene, have been investigated ...

  Citation × Citation Citation Abstract Copy Title: Pressure-induced insulating state in an organic superconductor Author: Gard, Gary L., Mohtasham, Javid, Schlueter, J. A., Pfleiderer, C., Wosnitza, J., Hagel, J. Year: 2003 The electronic-transport properties of the quasi-two-dimensional organic superconductor β″–(BEDT-TTF)₂SF₅CH₂CF₂SO₃, where BEDT-TTF stands for bisethylenedithio-tetrathiafulvalene, have been investigated in magnetic fields up to 15 T and under hydrostatic pressure up to about 14 kbars. Shubnikov–de Haas data reveal a nonmonotonic pressure dependence of the holelike Fermi surface, a roughly linear increase of the electron g factor, and an approximately linear decrease of the cyclotron effective mass. By assuming that the latter reflects the pressure-induced reduction of the superconducting coupling parameter λ the rapid reduction of the superconducting transition temperature Tc(p) can be reasonably well described by the modified McMillan equation. Above about 12 kbars the material becomes insulating with an activated resistive behavior. This first-order metal-insulator transition has a hysteresis of about 3 kbars. This unexpected behavior is assumed to be of structural origin, although clear changes of electronic band-structure properties precede the phase transition. Title: Pressure-induced insulating state in an organic superconductor Author: Gard, Gary L., Mohtasham, Javid, Schlueter, J. A., Pfleiderer, C., Wosnitza, J., Hagel, J. Year: 2003 The electronic-transport properties of the quasi-two-dimensional organic superconductor β″–(BEDT-TTF)₂SF₅CH₂CF₂SO₃, where BEDT-TTF stands for bisethylenedithio-tetrathiafulvalene, have been investigated in magnetic fields up to 15 T and under hydrostatic pressure up to about 14 kbars. Shubnikov–de Haas data reveal a nonmonotonic pressure dependence of the holelike Fermi surface, a roughly linear increase of the electron g factor, and an approximately linear decrease of the cyclotron effective mass. By assuming that the latter reflects the pressure-induced reduction of the superconducting coupling parameter λ the rapid reduction of the superconducting transition temperature Tc(p) can be reasonably well described by the modified McMillan equation. Above about 12 kbars the material becomes insulating with an activated resistive behavior. This first-order metal-insulator transition has a hysteresis of about 3 kbars. This unexpected behavior is assumed to be of structural origin, although clear changes of electronic band-structure properties precede the phase transition. Close

• 7. [Article] SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds

  The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure poL (atm) and enthalpy of vaporization Δ Hvap (kJ mol-1) of organic compounds as functions of temperature (T). ...

  Citation × Citation Citation Abstract Copy Title: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds Author: Pankow, James F., Asher, William E. Year: 2008 The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure poL (atm) and enthalpy of vaporization Δ Hvap (kJ mol-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log10poL,i (T)=∑kνk,ibk(T) where νk,i is the number of groups of type k, and bk (T) is the contribution to log10poL,i (T) by each group of type k. A zeroeth group is included that uses b0 (T) with ν0,i=1 for all i. A total of 30 structural groups are considered: molecular carbon, alkyl hydroxyl, aromatic hydroxyl, alkyl ether, alkyl ring ether, aromatic ether, aldehyde, ketone, carboxylic acid, ester, nitrate, nitro, alkyl amine (primary, secondary, and tertiary), aromatic amine, amide (primary, secondary, and tertiary), peroxide, hydroperoxide, peroxy acid, C=C, carbonylperoxynitrate, nitro-phenol, nitro-ester, aromatic rings, non-aromatic rings, C=C–C=O in a non-aromatic ring, and carbon on the acid-side of an amide. The T dependence in each of the bk (T) is assumed to follow b(T)=B1/T+B2+B3T+B4ln T. Values of the B coefficients are fit using an initial basis set of 272 compounds for which experimentally based functions po L,i=fi (T) are available. The range of vapor pressure considered spans fourteen orders of magnitude. The ability of the initially fitted B coefficients to predict poL values is examined using a test set of 184 compounds and a T range that is as wide as 273.15 to 393.15 K for some compounds. σFIT is defined as the average over all points of the absolute value of the difference between experimental and predicted values of log10poL,i (T). After consideration of σFIT for the test set, the initial basis set and test set compounds are combined, and the B coefficients re-optimized. For all compounds and temperatures, σFIT=0.34: on average, poL,i (T) values are predicted to within a factor of 2. Because d(log10 poL,i (T))d(1/T) is related to the enthalpy of vaporization ΔHvap,i, the fitted B provide predictions of ΔHvap,i based on structure. Title: SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds Author: Pankow, James F., Asher, William E. Year: 2008 The SIMPOL.1 group contribution method is developed for predicting the liquid vapor pressure poL (atm) and enthalpy of vaporization Δ Hvap (kJ mol-1) of organic compounds as functions of temperature (T). For each compound i, the method assumes log10poL,i (T)=∑kνk,ibk(T) where νk,i is the number of groups of type k, and bk (T) is the contribution to log10poL,i (T) by each group of type k. A zeroeth group is included that uses b0 (T) with ν0,i=1 for all i. A total of 30 structural groups are considered: molecular carbon, alkyl hydroxyl, aromatic hydroxyl, alkyl ether, alkyl ring ether, aromatic ether, aldehyde, ketone, carboxylic acid, ester, nitrate, nitro, alkyl amine (primary, secondary, and tertiary), aromatic amine, amide (primary, secondary, and tertiary), peroxide, hydroperoxide, peroxy acid, C=C, carbonylperoxynitrate, nitro-phenol, nitro-ester, aromatic rings, non-aromatic rings, C=C–C=O in a non-aromatic ring, and carbon on the acid-side of an amide. The T dependence in each of the bk (T) is assumed to follow b(T)=B1/T+B2+B3T+B4ln T. Values of the B coefficients are fit using an initial basis set of 272 compounds for which experimentally based functions po L,i=fi (T) are available. The range of vapor pressure considered spans fourteen orders of magnitude. The ability of the initially fitted B coefficients to predict poL values is examined using a test set of 184 compounds and a T range that is as wide as 273.15 to 393.15 K for some compounds. σFIT is defined as the average over all points of the absolute value of the difference between experimental and predicted values of log10poL,i (T). After consideration of σFIT for the test set, the initial basis set and test set compounds are combined, and the B coefficients re-optimized. For all compounds and temperatures, σFIT=0.34: on average, poL,i (T) values are predicted to within a factor of 2. Because d(log10 poL,i (T))d(1/T) is related to the enthalpy of vaporization ΔHvap,i, the fitted B provide predictions of ΔHvap,i based on structure. Close

• 8. [Article] Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission

  Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis ...

  Citation × Citation Citation Abstract Copy Title: Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission Author: Chiu, Sheng-Kuei, Manhat, Beth Ann, DeBenedetti, William J.I., Brown, Anna L., Fichter, Katye, Vu, Tania, Eastman, Micah, Jiao, Jun, Goforth, Andrea Mitchell Year: 2013 Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role in providing stable, aqueous, red-emitting Si NPs by (i) forming a hydrophobic barrier between the Si NPs and water and (ii) providing aqueous colloidal stability via the polar head group. We demonstrate preservation of the aqueous red emission of these Si NPs in biological media and examine the effects of pH on emission color. Title: Aqueous Red-Emitting Silicon Nanoparticles for Cellular Imaging: Consequences of Protecting Against Surface Passivation by Hydroxide and Water for Stable Red Emission Author: Chiu, Sheng-Kuei, Manhat, Beth Ann, DeBenedetti, William J.I., Brown, Anna L., Fichter, Katye, Vu, Tania, Eastman, Micah, Jiao, Jun, Goforth, Andrea Mitchell Year: 2013 Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role in providing stable, aqueous, red-emitting Si NPs by (i) forming a hydrophobic barrier between the Si NPs and water and (ii) providing aqueous colloidal stability via the polar head group. We demonstrate preservation of the aqueous red emission of these Si NPs in biological media and examine the effects of pH on emission color. Close