We present a protocol for creating a real-time movie of a molecular rotational wave packet using a high-resolution Coulomb explosion imaging setup.
We present a method for visualizing laser-induced, ultrafast molecular rotational wave packet dynamics. We have developed a new 2-dimensional Coulomb explosion imaging setup in which a hitherto-impractical camera angle is realized. In our imaging technique, diatomic molecules are irradiated with a circularly polarized strong laser pulse. The ejected atomic ions are accelerated perpendicularly to the laser propagation. The ions lying in the laser polarization plane are selected through the use of a mechanical slit and imaged with a high-throughput, 2-dimensional detector installed parallel to the polarization plane. Because a circularly polarized (isotropic) Coulomb exploding pulse is used, the observed angular distribution of the ejected ions directly corresponds to the squared rotational wave function at the time of the pulse irradiation. To create a real-time movie of molecular rotation, the present imaging technique is combined with a femtosecond pump-probe optical setup in which the pump pulses create unidirectionally rotating molecular ensembles. Due to the high image throughput of our detection system, the pump-probe experimental condition can be easily optimized by monitoring a real-time snapshot. As a result, the quality of the observed movie is sufficiently high for visualizing the detailed wave nature of motion. We also note that the present technique can be implemented in existing standard ion imaging setups, offering a new camera angle or viewpoint for the molecular systems without the need for extensive modification.
For a deeper understanding and better use of the dynamic nature of molecules, it is essential to clearly visualize molecular motions of interest. Time-resolved Coulomb explosion imaging is one of the powerful approaches to achieve this objective1,2,3. In this approach, the molecular dynamics of interest are initiated by a pump ultrashort laser field and are then probed by a time-delayed probe pulse. Upon probe irradiation, molecules are multiply ionized and broken into fragment ions due to the Coulomb repulsion. The spatial distribution of the ejected ions is a measure of the molecular structure and spatial orientation at the probe irradiation. A sequence of measurement scanning the pump-probe delay time leads to the creation of a molecular movie. It is noteworthy that, for the simplest case – diatomic molecules – the angular distribution of the ejected ions directly reflects the molecular axis distribution (i.e., the squared rotational wave function).
With regard to the pump process, recent progress in the coherent control of molecular motion using ultrashort laser fields has led to the creation of highly controlled rotational wave packets4,5. Furthermore, the direction of rotation can be actively controlled by using a polarization-controlled laser field6,7,8. It has therefore been expected that a detailed picture of molecular rotation, including wave natures, could be visualized when the Coulomb explosion imaging technique is combined with such a pump process9,10,11,12,13. However, we sometimes encounter experimental difficulties associated with the existing imaging methods, as mentioned below. The purpose of this paper is to present a new way of overcoming these difficulties and of creating a high-quality movie of molecular rotational wave packets. The first experimental movie of molecular rotation taken with the present method, along with its physical implications, were presented in our previous paper11. The background of development, the detailed theoretical aspect of the present imaging technique, and a comparison with other existing techniques will be given in a forthcoming paper. Here, we will mainly focus on the practical and technical aspects of the procedure, including the combination of the typical pump-probe optical setup and the new imaging apparatus. As in the previous paper, the target system is unidirectionally rotating nitrogen molecules11.
The main experimental difficulty of the existing imaging setup, schematically shown in Figure 1, has to do with the position of the detector, or the camera angle. Because the rotational axis coincides with the laser propagation axis6,7,8 in laser-field-induced molecular rotation, it is not practical to install a detector along the rotational axis. When the detector is installed so as to avoid laser irradiation, the camera angle corresponds to a side observation of rotation. In this case, it is impossible to reconstruct the original orientation of molecules from the projected (2D) ion image14. A 3D imaging detector14,15,16,17,18,19, with which the arrival time to the top detector and the ion impact positions can be measured, offered a unique way to directly observe molecular rotation using Coulomb explosion imaging10,12. However, the acceptable ion counts per laser shot are low (typically < 10 ions) in the 3D detector, meaning that it is difficult to create a long movie of molecular motion with high image quality14. The dead time of the detectors (typically ns) also affects the image resolution and imaging efficiency. It is also not a simple task to make a good pump-probe beam overlap by monitoring a real-time ion image with a laser repetition rate of <~1 kHz. Although several groups have observed rotational wave packets using the 3D technique, the spatial information was limited and/or direct, and a detailed visualization of wave nature, including complicated nodal structures, was not achieved10,12.
The essence of the new imaging technique is the use of the "new camera angle" in Figure 1. In this configuration, laser beam exposure to a detector is avoided while the 2D detector is parallel to the rotational plane, leading to the observation from the rotational axis direction. The slit allows only the ion in the rotational plane (the polarization plane of the laser pulses) to contribute to an image. A 2D detector, which offers a higher count rate (typically ~100 ions) than a 3D detector, can be used. The setup of the electronics is simpler than in the case of 3D detection, while the measurement efficiency is higher. Time-consuming mathematical reconstruction, such as Abel inversion14, is also not needed to extract angular information. These features lead to the easy optimization of the measurement system and to the production of high-quality movies. A standard 2D/3D charged-particle imaging apparatus can be easily modified to the present setup without the use of expensive equipment.
NOTE: Through this protocol, we clarify what we actually did to develop the present method. Exact parameters, including chamber and optical setup design and the sizes and types of the parts, are not always essential to apply the present system to the reader's apparatus. The essence of the procedures will be given as notes in each step.
1. Construction of a 2D-slice Imaging Apparatus
NOTE: Throughout this step, all the commercially available parts and equipment, such as a vacuum pump and a detector, are installed according to the manufacturer's instructions or user's manuals.
2. Construction of a Pump-probe Optical Setup
NOTE: For this step, see Figure 3 to understand where and how the following steps are carried out. The purpose of this step is to create three collinear fs pulses from a commercial Ti:sapphire laser amplifier for the pump-probe experiment11. The first pulse was for molecular alignment (linearly polarized, center wavelength of 820 nm, peak intensity <30 TW/cm2), the second was for the direction control (a delayed replica of the first one, except for the linear polarization +45° tilted from the polarization axis of the first pulse), and the third was the Coulomb explosion imaging probe (circularly polarized, 407 nm, 100 fs, 600 TW/cm2). Throughout this step, all the commercially available parts and equipment, such as a polarization checker and an optical stage, are installed and used according to the manufacturer's instructions or user's manuals.
NOTE: Throughout this step, all the optical components are installed and used according to the standard procedures of optical experiments and the manufacturer's guide for optics. All the turning and dichroic mirrors used are dielectric multilayer mirrors in order to avoid laser power loss during the many reflections in the optical path. Some of the optics and crystals used are shown in the material list for this article.
3. Setup for a Measurement System
NOTE: Throughout this step, all the commercially available parts and equipment, such as a power supply and delay generators, are installed and used according to the manufacturer's instructions or user's manuals.
4. Measurements
NOTE: The measurement method used here is a combination of reported procedures14,27 and the present imaging setup. Throughout this step, all the commercially available parts and equipment, such as high-voltage electronics, are installed and used according to the manufacturer's instructions or user's manuals.
Figure 4A shows a probe-only raw image of the N2+ ion ejected upon probe irradiation (Coulomb explosion), taken for one probe laser shot. Each bright spot corresponds to one ion. Figure 4B shows a summed image of 10,000 binarized raw camera images. These images show that our imaging setup can monitor the molecules of all the orientation angles in the polarization plane. Figure 4C shows the normalized polar plot corresponding to that of Figure 4B. Because the rotational control (pump) pulse was absent, the distribution is isotropic (Figure 4C shows a circle).
In Figure 4B, a small defect due to detector inhomogeneity can be seen in the bottom of the ellipse. Such a defect always appears in the same position of the image. Therefore, it can be compensated for by normalizing the observed images with a probe-only image (step 4.5.3.7).
Figure 5 shows selected snapshots taken after the irradiation of the two pump pulses. So as to improve understanding, not only the observed ion images, but also the corresponding polar plots and "dumbbell" model pictures are shown as a function of probe time. The polar plots are created in step 4.5.3.5. The dumbbell picture is an overlapped image of dumbbells of various orientation angles, and their weights (opacity) are the observed angular probabilities. The sequence of images forms a clear movie of unidirectional molecular rotation. The wave nature of motion can be seen as the complicated nodal structures and the dispersion, including an "X"-shape formation.
Figure 6 shows an ion image taken with a damaged slit and a photograph of the slit edge with a dent. A small defect largely affects the observed image. In such a case, repeating step 1.5 is required. This fact is also discussed in the discussion section.
Figure 7 shows the raw camera image at the optimized pump-probe overlap condition. By monitoring such a beam overlap signal, the optical paths can be optimized. This leads to a clear movie, as in Figure 5.
Figure 1: Conceptual diagram of the camera angles in the impractical, typical, and new configurations. In the typical camera angle, a detector is installed to avoid laser exposure, but the ejection angles of ions cannot be reconstructed from the 2D projected image. In the present, new camera angle, the rotational plane (laser polarization plane) is parallel to the detector surface and is therefore suitable for visualizing the rotational motion. Typical bias voltages are 2,500 V, 1,799 V, 1,846 V, 253 V, 0 V, 3,500 V, -800 V, and 4,500 V for ion optics 1, 2, 3, 4, and 5, the pulsed repeller, the microchannel plates, and the phosphor screen, respectively. The ion optics numbering starts at the bottom electrode. Please click here to view a larger version of this figure.
Figure 2: Schematic diagrams of the 2D imaging unit. (A) Schematic diagram of the detector assembly. A circle plate colored in orange is a baseplate to which the other parts are mounted with bolts. (B) Schematic diagram of the slit assembly. The right picture explains the motion of the slit. The size values are in mm. Please click here to view a larger version of this figure.
Figure 3: Schematic diagram of the present pump-probe optical setup. The optical paths of the pump pulses for rotational excitation are illustrated by the red lines, while that of the probe (imaging) pulse is shown by the blue line. NLC, nonlinear crystal for second-harmonic generation; HWP, half-waveplate; QWP, quarter-waveplate; DM, dichroic mirror; BS, 50:50 beam splitter; HRM: high-resolution mirror mount. Please click here to view a larger version of this figure.
Figure 4: Raw and analyzed Coulomb exploded ion images. (A) A typical raw image of N2+ taken for one probe shot. (B) Summed image for 10,000 binarized camera images. The size of the camera image is 1,200 x 750 pixels. The corresponding real-space size is 80 mm x 50 mm. (C) The normalized polar plot constructed from the summed image. In the raw and summed images, false color was added to show the signal intensity. The polar angles in degrees are shown along the circumference. The radial value is an angle-dependent probability (arbitrary unit). Please click here to view a larger version of this figure.
Figure 5: Selected snapshots of the laser-induced rotational wave packet dynamics. In each time delay, the upper panel shows the ion image in which the elliptical shape has been converted to a circle. The middle panel shows the corresponding polar plot. The bottom panel shows a dumbbell model of the angular distribution. This dumbbell picture is an overlapped image of dumbbells from various orientation angles, and their weights (opacity) are the observed angular probabilities. The polar plot uses the same unit and scale as in Figure 4. The ion image employs transformed coordinates, as in step 4.5.3.4. Please click here to view a larger version of this figure.
Figure 6: Effect of the slit defect on the experimental ion image. (A) Observed probe-only N2+ ion image taken with a damaged slit. (B) Photograph of the slit edge having a sub-mm dent. Please click here to view a larger version of this figure.
Figure 7: Raw camera image at the optimized pump-probe overlap condition. The probe time is set at t = 4.0 ps after the first pump pulse irradiation. At this time, the maximum degree of molecular alignment is achieved. The size of the camera image is 1,200 x 750 pixels. The corresponding real-space size is 80 mm x 50 mm. Please click here to view a larger version of this figure.
The present procedure enables us to capture a real-time movie of molecular rotation with a slit-based 2D imaging setup. Because the observed ions pass through the slit, step 1.5 is one of the critical steps. The edges of the slit blades must be sharp. When there is a small defect, such as a 0.3 mm dent in the slit, a scratch is observed in the ion image (Figure 6). In such a case, the slit blade should be polished with 2,000-grit wet sandpaper.
Apart from the unique camera angle shown in Figure 1, this method has several advantages over the 3D imaging detector, which was previously the only solution for rotational wave packet imaging.
First, in the present procedure, optical beam alignment can be carried out easily by monitoring raw ion images, as in steps 4.1-4.2. Figure 7 shows the raw camera image at the optimized pump-probe overlap condition. When the pump-probe beam overlap is lost, anisotropic or enhanced image signatures cannot be seen, as in Figure 4A. This fact emphasizes the importance of steps 4.1-4.2 in the present method. Because the spot sizes of the pump and probe beams are on the order of 10 µm, it is generally difficult to find an optimal overlap condition without monitoring real-time images. In the case of a 3D imaging detector, several seconds are required to form an image with sufficient data points (at least 1,000 ions) when a 1,000 Hz or lower repetition-rate laser is employed, because the count rate is limited to a few events per laser shot in the 3D detector. In the present method, on the other hand, the count rate is essentially unlimited, and the number of ions per frame can be increased simply by extending the exposure time. In the present case, more than 1,000 ions are detected within the 50 ms exposure time.
The high count rate of the present method also leads to a shorter data acquisition time. Because the frame rate of the camera is 250 fps, it takes only ~40 s to take one snapshot of the molecular motion at a particular time. For the measurement over the one molecular rotational revival time (~8.4 ps) with a ~33-fs step, the measurement time is only a few hours. This is another advantage, because experimental data would be degraded by the limited long-term stability of the lasers and the entire experimental setup. In our setup, for example, time duration changes with time, partly due to the temperature change in the fs amplifier. A 3-K change within 6 h resulted in the thermal expansion of the amplifier, including the elongation of the distance between the pulse compressor gratings, leading to the elongation of the pulse duration31. Laser-beam drift, which degrades the signal of the pump-induced dynamics, was also detected within ~8 h, although the origin of this drift was not identified.
The present technique is a type of 2D imaging, limiting the information in 3D. In the case of a Coulomb explosion, only the fragment of ions ejected in the detection plane contribute to the image. This implies that it is difficult to apply the present method directly to complicated fragmentation processes, such as those involved in coincidence imaging studies25,32,33. We note that the sum of the signal intensity with our method is proportional to the probability in the detection plane. This represents indirect information on the dimension not included in the imaging plane11,12.
While we focus on Coulomb explosion imaging in this paper, the present approach can be, in principle, applied to general charged-particle imaging, such as that involved in photodissociation studies14. In the existing imaging procedure, to obtain a 2D tomogram of a 3D Newton sphere of charged particles, the polarization of light should be parallel to the detector surface. In other words, the camera angle is limited to particular conditions. Also, in the present 2D imaging technique, a 3D ion cloud is spatially sliced to a 2D cut and is then imaged. With this slice imaging, the freedom of the camera angle will open a way to obtain hitherto-unobserved information that sometimes appears in the laser propagation direction26,34.
The authors have nothing to disclose.
This work was supported in part by grants-in-aid KAKENHI from the Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) Japan (#26104539, #26620020, #26810011, #15H03766, #15KT0060, #16H00826, and #16K13927); the Konica Minolta Science and Technology Foundation; the “Planting Seeds for Research” program of TokyoTech; the Imaging Science Project of the Center for Novel Science Initiatives (CNSI) at the National Institutes of Natural Sciences (NINS) (#IS261006); the RIKEN-IMS joint program on “Extreme Photonics;” and the Consortium for Photon Science and Technology (CPhoST).
CMOS camera | Toshiba TELI | BU-238M-ES | equipped with SONY IMX174 sensor |
High voltage switch | Behlke | HTS-41-03-GSM | |
High voltage switch | Behlke | HTS-80-03 | |
Digital delay generator | Stanford research systems | DG535 | |
Digital delay generator | Stanford research systems | DG645 | |
Microchannel plate | Photonis | 3075 | |
Pulsed valve | LAMID LTD | Even-Lavie valve | High repetition, room temperature model |
Molecular beam skimmers | Institute for Molecular Science | 13C11 | 3 and 1.5 mm center hole, 25 degrees full inner angle, and ~50 mm length |
Optical Comparator | Nikon | V-24B | |
DPSS laser | Lighthouse Photonics | Sprout | |
Femtosecond Ti:Sapphire oscillator | KMLabs | Halcyon | |
Femtosecond Ti:Sapphire amplifier | Quantronix | Odin-II HE | |
Motorized linear stage | Sigma Koki | KST(GS)-100X | |
Manual X-stage | Sigma Koki | TSD-601S | |
High resolution mirror mount | Newport | Suprema SX100-F2KN-254 | |
High resolution mirror mount | LIOP-TEC GmbH | SR100-100R-2-HS | |
Polarization checker | Paradigm Devices, Inc. | O-tool VIS | |
Instrument communication interface | National Instruments | NI-MAX | |
Graphical development environment for measurement programs | National Instruments | LabVIEW 2014 | |
Laser line dielectric mirror | CVI/LEO | TLM2-400/800-45UNP | |
Laser line dielectric mirror | Altechna | Low GDD Ultrafast mirror | |
Laser line dielectric mirror | Altechna | Low GDD Ultrafast mirror | |
Femtosecond polarizer | Advanced Thin Films | PBS-GVD |